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Sample records for re4q4x124 cluster complexes

  1. Formation of Cluster Complexes by Cluster-Cluster-Collisions

    NASA Astrophysics Data System (ADS)

    Ichihashi, Masahiko; Odaka, Hideho

    2015-03-01

    Multi-element clusters are interested in their chemical and physical properties, and it is expected that they are utilized as catalysts, for example. Their properties critically depend on the size, composition and atomic ordering, and it should be important to adjust the above parameters for their functionality. One of the ways to form a multi-element cluster is to employ a low-energy collision between clusters. Here, we show characteristic results obtained in the collision between a neutral Ar cluster and a size-selected Co cluster ion. Low-energy collision experiment was accomplished by using a newly developed merging-beam apparatus. Cobalt cluster ions were produced by laser ablation, and mass-selected. On the other hand, argon clusters were prepared by the supersonic expansion of Ar gas. Both cluster beams were merged together in an ion guide, and ionic cluster complexes were mass-analyzed. In the collision of Co2+ and ArN, Co2Arn+ (n = 1 - 30) were observed, and the total intensity of Co2Arn+ (n >= 1) is inversely proportional to the relative velocity between Co2+ and ArN. This suggests that the charge-induced dipole interaction between Co2+ and a neutral Ar cluster is dominant in the formation of the cluster complex, Co2+Arn.

  2. Atomic clusters with addressable complexity

    NASA Astrophysics Data System (ADS)

    Wales, David J.

    2017-02-01

    A general formulation for constructing addressable atomic clusters is introduced, based on one or more reference structures. By modifying the well depths in a given interatomic potential in favour of nearest-neighbour interactions that are defined in the reference(s), the potential energy landscape can be biased to make a particular permutational isomer the global minimum. The magnitude of the bias changes the resulting potential energy landscape systematically, providing a framework to produce clusters that should self-organise efficiently into the target structure. These features are illustrated for small systems, where all the relevant local minima and transition states can be identified, and for the low-energy regions of the landscape for larger clusters. For a 55-particle cluster, it is possible to design a target structure from a transition state of the original potential and to retain this structure in a doubly addressable landscape. Disconnectivity graphs based on local minima that have no direct connections to a lower minimum provide a helpful way to visualise the larger databases. These minima correspond to the termini of monotonic sequences, which always proceed downhill in terms of potential energy, and we identify them as a class of biminimum. Multiple copies of the target cluster are treated by adding a repulsive term between particles with the same address to maintain distinguishable targets upon aggregation. By tuning the magnitude of this term, it is possible to create assemblies of the target cluster corresponding to a variety of structures, including rings and chains.

  3. Competitive cluster growth in complex networks

    NASA Astrophysics Data System (ADS)

    Moreira, André A.; Paula, Demétrius R.; Costa Filho, Raimundo N.; Andrade, José S., Jr.

    2006-06-01

    In this work we propose an idealized model for competitive cluster growth in complex networks. Each cluster can be thought of as a fraction of a community that shares some common opinion. Our results show that the cluster size distribution depends on the particular choice for the topology of the network of contacts among the agents. As an application, we show that the cluster size distributions obtained when the growth process is performed on hierarchical networks, e.g., the Apollonian network, have a scaling form similar to what has been observed for the distribution of a number of votes in an electoral process. We suggest that this similarity may be due to the fact that social networks involved in the electoral process may also possess an underlining hierarchical structure.

  4. A graph clustering method for community detection in complex networks

    NASA Astrophysics Data System (ADS)

    Zhou, HongFang; Li, Jin; Li, JunHuai; Zhang, FaCun; Cui, YingAn

    2017-03-01

    Information mining from complex networks by identifying communities is an important problem in a number of research fields, including the social sciences, biology, physics and medicine. First, two concepts are introduced, Attracting Degree and Recommending Degree. Second, a graph clustering method, referred to as AR-Cluster, is presented for detecting community structures in complex networks. Third, a novel collaborative similarity measure is adopted to calculate node similarities. In the AR-Cluster method, vertices are grouped together based on calculated similarity under a K-Medoids framework. Extensive experimental results on two real datasets show the effectiveness of AR-Cluster.

  5. Motion of clusters on complex surfaces

    NASA Astrophysics Data System (ADS)

    Alkis, Sabri; Krause, Jeffrey; Cheng, Hai-Ping

    2007-03-01

    Polymer and organic molecule assemblies have been investigated intensely in the past decade, due to their vast range of applications in nano-molecular electronics and as bio-sensors. In particular, self-assembled monolyers (SAMs) of alkanethiol on the Au(111) surface are used widely in surface studies because they are simple structurally, stable thermodynamically and have well-defined order. In this project, inspired by recent experiments, we use classical molecular dynamics simulations to study motions of Agn clusters with various sizes on the alkanthiol SAMs. We report detailed results on dynamics, diffusion, and sintering processes of these nano-clusters.

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

    NASA Astrophysics Data System (ADS)

    Bekki, Kenji

    2017-01-01

    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 onto 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] × 105M⊙ can accrete more than 105M⊙ gas from AGB stars of the SCC. We suggest that merging of hierarchical star cluster complexes can play key roles in stellar halo formation around GCs and self-enrichment processes in the early phase of GC formation.

  7. Symmetries, Cluster Synchronization, and Isolated Desynchronization in Complex Networks

    NASA Astrophysics Data System (ADS)

    Pecora, Louis

    2015-03-01

    Many networks are observed to produce patterns of synchronized clusters, but it has been difficult to predict these clusters in general or understand the conditions for their formation. We show the intimate connection between network symmetry and cluster synchronization. We apply computational group theory to reveal the clusters and determine their stability. In complex networks the symmetries can number in the millions, billions, and more. The connection between symmetry and cluster synchronization is experimentally explored using an electro-optic network. We observe and explain a surprising and common phenomenon (isolated desynchronization) in which some clusters lose synchrony while leaving others connected to them synchronized. We show the isolated desynchronization is intimately related to the decomposition of the group of symmetries into subgroups. The results could guide the design of new power grid systems or lead to new understanding of the dynamical behavior of networks ranging from neural to social.

  8. Cellular uptake and cytotoxicity of octahedral rhenium cluster complexes.

    PubMed

    Choi, Soo-Jin; Brylev, Konstantin A; Xu, Jing-Zhe; Mironov, Yuri V; Fedorov, Vladimir E; Sohn, Youn Soo; Kim, Sung-Jin; Choy, Jin-Ho

    2008-11-01

    Cellular uptake behavior of a novel class of octahedral rhenium cluster compounds, hexahydroxo complexes K(4)[{Re(6)S(8)}(OH)(6)].8H(2)O (1) and K(4)[{Re(6)Se(8)}(OH)(6)].8H(2)O (2), was evaluated in human cervical adenocarcinoma HeLa cells. Confocal microscopy and flow cytometry studies demonstrated that rhenium cluster 1 was not internalized into cell, while rhenium cluster 2 was. Conjugation of a polymer to rhenium cluster 1, namely the derivative K(4)[{Re(6)S(8)}(OH)(5)L] (3) (L is amphiphilic diblock copolymer MPEG550-CH(2)CONH-GlyPheLeuGlyPheLeu-COO(-)), considerably enhanced cellular uptake in a concentration-dependent manner and was predominantly localized in the cytoplasm and nucleus upon incubation time. The uptake of rhenium cluster 2 was mediated by energy-dependent endocytosis, whereas rhenium cluster 3 was directly ingested into cells by cell-fusion-like mechanism. According to the cytotoxicity evaluation test, both rhenium clusters 2 and 3 did not exhibit acute cytotoxic effects up to 50 microM, at the practical concentration level of biological applications. It is, therefore, expected that the rhenium cluster complexes can be promising potential candidates as diagnostic agents for medical treatment.

  9. Nucleoside modification with boron clusters and their metal complexes.

    PubMed

    Wojtczak, Blazej A; Olejniczak, Agnieszka B; Lesnikowski, Zbigniew J

    2009-09-01

    General methods for the synthesis of nucleosides modified with borane clusters and metallacarborane complexes are presented. These include: (1) the click chemistry approach based on Huisgen 1,3-dipolar cycloaddition and (2) tethering of the metallacarborane group to the aglycone of a nucleoside via a dioxane ring opening in oxonium metallacarborane derivatives. The proposed methodologies broaden the availability of nucleoside-borane cluster conjugates and open up new areas for their applications.

  10. Ionization reactions of ion complexes in mesoscopic water clusters

    NASA Astrophysics Data System (ADS)

    Consta, Styliani; Kapral, Raymond

    1999-12-01

    The free energy and dynamics of the dissociation reactions of the [Na+(Cl-)2] ion complex in mesoscopic water clusters are examined. The free energy surface shows the existence of stable single and double solvent-separated complex species formed from ionization of the stable double-contact ion complex. The reaction occurs on the cluster surface for mesoscale clusters composed of tens of water molecules. Passage between stable species is an activated process but barrier crossing has a large diffusive component so that dynamical corrections to transition state theory are large. The structure of the decay of the time-dependent rate constant reflects the diffusive character of the recrossing dynamics so that a plateau is not established on a 10 ps time scale in contrast to ionization dynamics in bulk fluids.

  11. Mathematical modelling of complex contagion on clustered networks

    NASA Astrophysics Data System (ADS)

    O'sullivan, David J.; O'Keeffe, Gary; Fennell, Peter; Gleeson, James

    2015-09-01

    The spreading of behavior, such as the adoption of a new innovation, is influenced bythe structure of social networks that interconnect the population. In the experiments of Centola (Science, 2010), adoption of new behavior was shown to spread further and faster across clustered-lattice networks than across corresponding random networks. This implies that the “complex contagion” effects of social reinforcement are important in such diffusion, in contrast to “simple” contagion models of disease-spread which predict that epidemics would grow more efficiently on random networks than on clustered networks. To accurately model complex contagion on clustered networks remains a challenge because the usual assumptions (e.g. of mean-field theory) regarding tree-like networks are invalidated by the presence of triangles in the network; the triangles are, however, crucial to the social reinforcement mechanism, which posits an increased probability of a person adopting behavior that has been adopted by two or more neighbors. In this paper we modify the analytical approach that was introduced by Hebert-Dufresne et al. (Phys. Rev. E, 2010), to study disease-spread on clustered networks. We show how the approximation method can be adapted to a complex contagion model, and confirm the accuracy of the method with numerical simulations. The analytical results of the model enable us to quantify the level of social reinforcement that is required to observe—as in Centola’s experiments—faster diffusion on clustered topologies than on random networks.

  12. Encounter Complexes for Clustering Network Flow (Briefing Charts)

    DTIC Science & Technology

    2015-01-01

    JAN 2015 2. REPORT TYPE 3. DATES COVERED 00-00-2015 to 00-00-2015 4. TITLE AND SUBTITLE Encounter Complexes For Clustering Network Flow 5a...2015. 14. ABSTRACT 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT Same as Report (SAR) 18. NUMBER OF PAGES 37

  13. Clustering determines the dynamics of complex contagions in multiplex networks

    NASA Astrophysics Data System (ADS)

    Zhuang, Yong; Arenas, Alex; Yaǧan, Osman

    2017-01-01

    We present the mathematical analysis of generalized complex contagions in a class of clustered multiplex networks. The model is intended to understand spread of influence, or any other spreading process implying a threshold dynamics, in setups of interconnected networks with significant clustering. The contagion is assumed to be general enough to account for a content-dependent linear threshold model, where each link type has a different weight (for spreading influence) that may depend on the content (e.g., product, rumor, political view) that is being spread. Using the generating functions formalism, we determine the conditions, probability, and expected size of the emergent global cascades. This analysis provides a generalization of previous approaches and is especially useful in problems related to spreading and percolation. The results present nontrivial dependencies between the clustering coefficient of the networks and its average degree. In particular, several phase transitions are shown to occur depending on these descriptors. Generally speaking, our findings reveal that increasing clustering decreases the probability of having global cascades and their size, however, this tendency changes with the average degree. There exists a certain average degree from which on clustering favors the probability and size of the contagion. By comparing the dynamics of complex contagions over multiplex networks and their monoplex projections, we demonstrate that ignoring link types and aggregating network layers may lead to inaccurate conclusions about contagion dynamics, particularly when the correlation of degrees between layers is high.

  14. Structural and functional clusters of complex brain networks

    NASA Astrophysics Data System (ADS)

    Zemanová, Lucia; Zhou, Changsong; Kurths, Jürgen

    2006-12-01

    Recent research using the complex network approach has revealed a rich and complicated network topology in the cortical connectivity of mammalian brains. It is of importance to understand the implications of such complex network structures in the functional organization of the brain activities. Here we study this problem from the viewpoint of dynamical complex networks. We investigate synchronization dynamics on the corticocortical network of the cat by modeling each node (cortical area) of the network with a sub-network of interacting excitable neurons. We find that the network displays clustered synchronization behavior, and the dynamical clusters coincide with the topological community structures observed in the anatomical network. Our results provide insights into the relationship between the global organization and the functional specialization of the brain cortex.

  15. The bithorax complex of Drosophila an exceptional Hox cluster.

    PubMed

    Maeda, Robert K; Karch, François

    2009-01-01

    In his 1978 seminal paper, Ed Lewis described a series of mutations that affect the segmental identities of the segments forming the posterior two-thirds of the Drosophila body plan. In each class of mutations, particular segments developed like copies of a more-anterior segment. Genetic mapping of the different classes of mutations led to the discovery that their arrangement along the chromosome paralleled the body segments they affect along the anteroposterior axis of the fly. As all these mutations mapped to the same cytological location, he named this chromosomal locus after its founding mutation. Thus the first homeotic gene (Hox) cluster became known as the bithorax complex (BX-C). Even before the sequencing of the BX-C, the fact that these similar mutations grouped together in a cluster, lead Ed Lewis to propose that the homeotic genes arose through a gene duplication mechanism and that these clusters would be conserved through evolution. With the identification of the homeobox in the early 1980s, Lewis' first prediction was confirmed. The two cloned Drosophila homeotic genes, Antennapedia and Ultrabithorax, were indeed related genes. Using the homeobox as an entry point, homologous genes have since been cloned in many other species. Today, Hox clusters have been discovered in almost all metazoan phyla, confirming Lewis' second prediction. Remarkably, these homologous Hox genes are also arranged in clusters with their order within each cluster reflecting the anterior boundary of their domain of expression along the anterior-posterior axis of the animal. This correlation between the genomic organization and the activity along the anteroposterior body axis is known as the principle of "colinearity." The description of the BX-C inspired decades of developmental and evolutionary biology. And although this first Hox cluster led to the identification of many important features common to all Hox gene clusters, it now turns out that the fly Hox clusters are rather

  16. The globular cluster system of NGC 1316. III. Kinematic complexity

    NASA Astrophysics Data System (ADS)

    Richtler, T.; Hilker, M.; Kumar, B.; Bassino, L. P.; Gómez, M.; Dirsch, B.

    2014-09-01

    discernable out to 3' radius. The kinematic major axis of NGC 1316 is misaligned by about 10° with the photometric major axis, which might indicate a triaxial symmetry. A simple spherical model like that suggested by dynamical analyses of planetary nebulae also reproduces the velocity dispersions of the faint globular clusters. Conclusions: The central dark matter density of the present model resembles a giant elliptical galaxy. This contradicts population properties which indicate spiral galaxies as pre-merger components. Modified Newtonian dynamics (MOND) would provide a solution, but the kinematical complexity of NGC 1316 does not allow a really firm conclusion. However, NGC 1316 might anyway be a problem for a cold dark matter scenario, if the high dark matter density in the inner region is confirmed in future studies. Based on observations obtained with the VLT at ESO, Cerro Paranal, Chile under the programme 078.B-0856.Appendices are available in electronic form at http://www.aanda.org

  17. Knockout driven reactions in complex molecules and their clusters

    NASA Astrophysics Data System (ADS)

    Gatchell, Michael; Zettergren, Henning

    2016-08-01

    Energetic ions lose some of their kinetic energy when interacting with electrons or nuclei in matter. Here, we discuss combined experimental and theoretical studies on such impulse driven reactions in polycyclic aromatic hydrocarbons (PAHs), fullerenes, and pure or mixed clusters of these molecules. These studies show that the nature of excitation is important for how complex molecular systems respond to ion/atom impact. Rutherford-like nuclear scattering processes may lead to prompt atom knockout and formation of highly reactive fragments, while heating of the molecular electron clouds in general lead to formation of more stable and less reactive fragments. In this topical review, we focus on recent studies of knockout driven reactions, and present new calculations of the angular dependent threshold (displacement) energies for such processes in PAHs. The so-formed fragments may efficiently form covalent bonds with neighboring molecules in clusters. These unique molecular growth processes may be important in astrophysical environments such as low velocity shock waves.

  18. 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.

  19. Thiol surface complexation on growing CdS clusters

    SciTech Connect

    Swayambunathan, V.; Hayes, D.; Schmidt, K.H.; Liao, Y.X.; Meisel, D. )

    1990-05-09

    The growth of small CdS colloidal particles has been initiated by pulse radiolytic release of sulfide from thiol (3-mercapto-1,2-propanediol, RSH) in the presence of Cd{sup 2+} ions. The kinetics and stoichiometry of the ensuring reactions were followed by conductivity, absorption spectroscopy, and light-scattering techniques. The final CdS product has been identified by electron diffraction. The formation of Cd-thiolate complexes at the surface of the particles is indicated by conductivity and by energy dispersive analysis of X-ray (EDAX) results. The rate of formation of CdS clusters is strongly pH dependent due to the pH effect on the stability of Dd{sup 2+}/HS{sup {minus}} complexes. At low pHs (4.0-5.3) the growth mechanism is proposed to be primarily a cluster-molecule process. At this pH range Cd{sup 2+} ions at the CdS particle surface complex with thiolate ions stronger than in the bulk of the solution. The size control of the particles by thiols is proposed to result from a competition of thiolate ions with HS{sup {minus}} ions for cadmium ions at the surface of the growing particles.

  20. Fuzzy nodes recognition based on spectral clustering in complex networks

    NASA Astrophysics Data System (ADS)

    Ma, Yang; Cheng, Guangquan; Liu, Zhong; Xie, Fuli

    2017-01-01

    In complex networks, information regarding the nodes is usually incomplete because of the effects of interference, noise, and other factors. This results in parts of the network being blurred and some information having an unknown source. In this paper, a spectral clustering algorithm is used to identify fuzzy nodes and solve network reconstruction problems. By changing the fuzzy degree of placeholders, we achieve various degrees of credibility and accuracy for the restored network. Our approach is verified by experiments using open source datasets and simulated data.

  1. Heptanuclear lanthanide [Ln7] clusters: from blue-emitting solution-stable complexes to hybrid clusters.

    PubMed

    Canaj, Angelos B; Tsikalas, George K; Philippidis, Aggelos; Spyros, Apostolos; Milios, Constantinos J

    2014-09-07

    The use of LH3 (2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol) and aibH (2-amino-isobutyric acid) in 4f chemistry has led to the isolation of eight new isostructural lanthanide complexes. More specifically, the reaction of the corresponding lanthanide nitrate salt with LH3 and aibH in MeOH, under solvothermal conditions in the presence of NEt3, led to the isolation and characterization of seven complexes with the general formulae [Ln(III)7(OH)2(L')9(aib)]·4MeOH (Ln = Gd, ·4MeOH; Tb, ·4MeOH; Dy, ·4MeOH; Ho, ·4MeOH; Er, ·4MeOH; Tm, ·4MeOH; Yb, ·4MeOH L' = the dianion of the Schiff base between naphthalene aldehyde and 2-amino-isobutyric acid). Furthermore, the isostructural Y(III) analogue, cluster [Y(III)7(OH)2(L')9(aib)]·4MeOH (·4MeOH), was synthesized in a similar manner to . The structure of all eight clusters describes a distorted [M(III)6] octahedron which encapsulates a seventh M(III) ion in an off-centre fashion. Dc magnetic susceptibility studies in the 5-300 K range for complexes reveal the presence of dominant antiferromagnetic exchange interactions within the metallic clusters as evidenced by the negative Weiss constant, θ, while ac magnetic susceptibility measurements show temperature and frequency dependent out-of-phase signals for the [Dy(III)7] analogue (·4MeOH), suggesting potential single molecule magnetism character. Furthermore, for complex , simulation of its dc magnetic susceptibility data yielded very weak antiferromagnetic interactions within the metallic centres. Solid-state emission studies for all clusters display ligand-based emission, while extended 1D and 2D NMR studies for ·4MeOH reveal that the species retain their structural integrity in solution. In addition, TGA measurements for , and revealed excellent thermal stability up to 340 °C for the clusters.

  2. Invariant Chain Complexes and Clusters as Platforms for MIF Signaling.

    PubMed

    Lindner, Robert

    2017-02-10

    Invariant chain (Ii/CD74) has been identified as a surface receptor for migration inhibitory factor (MIF). Most cells that express Ii also synthesize major histocompatibility complex class II (MHC II) molecules, which depend on Ii as a chaperone and a targeting factor. The assembly of nonameric complexes consisting of one Ii trimer and three MHC II molecules (each of which is a heterodimer) has been regarded as a prerequisite for efficient delivery to the cell surface. Due to rapid endocytosis, however, only low levels of Ii-MHC II complexes are displayed on the cell surface of professional antigen presenting cells and very little free Ii trimers. The association of Ii and MHC II has been reported to block the interaction with MIF, thus questioning the role of surface Ii as a receptor for MIF on MHC II-expressing cells. Recent work offers a potential solution to this conundrum: Many Ii-complexes at the cell surface appear to be under-saturated with MHC II, leaving unoccupied Ii subunits as potential binding sites for MIF. Some of this work also sheds light on novel aspects of signal transduction by Ii-bound MIF in B-lymphocytes: membrane raft association of Ii-MHC II complexes enables MIF to target Ii-MHC II to antigen-clustered B-cell-receptors (BCR) and to foster BCR-driven signaling and intracellular trafficking.

  3. Invariant Chain Complexes and Clusters as Platforms for MIF Signaling

    PubMed Central

    Lindner, Robert

    2017-01-01

    Invariant chain (Ii/CD74) has been identified as a surface receptor for migration inhibitory factor (MIF). Most cells that express Ii also synthesize major histocompatibility complex class II (MHC II) molecules, which depend on Ii as a chaperone and a targeting factor. The assembly of nonameric complexes consisting of one Ii trimer and three MHC II molecules (each of which is a heterodimer) has been regarded as a prerequisite for efficient delivery to the cell surface. Due to rapid endocytosis, however, only low levels of Ii-MHC II complexes are displayed on the cell surface of professional antigen presenting cells and very little free Ii trimers. The association of Ii and MHC II has been reported to block the interaction with MIF, thus questioning the role of surface Ii as a receptor for MIF on MHC II-expressing cells. Recent work offers a potential solution to this conundrum: Many Ii-complexes at the cell surface appear to be under-saturated with MHC II, leaving unoccupied Ii subunits as potential binding sites for MIF. Some of this work also sheds light on novel aspects of signal transduction by Ii-bound MIF in B-lymphocytes: membrane raft association of Ii-MHC II complexes enables MIF to target Ii-MHC II to antigen-clustered B-cell-receptors (BCR) and to foster BCR-driven signaling and intracellular trafficking. PMID:28208600

  4. Synthesis of supramolecular iron (III) complexes by cluster aggregation

    NASA Astrophysics Data System (ADS)

    Seddon, Elisa Joy

    2000-12-01

    Biologically, iron is a ubiquitous and versatile metal, found in the active sites of proteins responsible for both oxygen and electron transport. Multinuclear iron-oxo proteins are either dinuclear, or contain many iron atoms; the [Fe2O] unit occurs in hemerythrin (Hr), ribonucleotide reductase, purple acid phosphatase (POP) and methane monooxygenase (MMO), whereas ferritin (Ft) can store up to 4500 iron atoms. Iron storage and transport are essential for protecting biological organisms from free iron, since free Fe(II) ions, will react with dioxygen to form destructive organic radicals, and free Fe(III) ions form insoluble iron hydroxide aggregates under physiological conditions. The tendency of iron to form molecular aggregates in systems containing water or alcohol, together with the fact that each iron atom possesses a large number of unpaired electrons (5 for high-spin FeIII) often results in products possessing large spin ground states (S). The current record-holder for iron is a Fe19 complex, with at least 33 unpaired electrons in the ground state (S = 33/2). Hence, iron is also important in the rapidly developing field of molecular magnetic materials. For these two reasons, the preparation of iron clusters with new topologies and properties has become a major goal of many synthetic inorganic groups, including our own. In this thesis work, synthetic and spectroscopic methods of inorganic coordination chemistry were used to achieve two different goals: firstly, to synthesize dinuclear iron complexes with the use of tetradentate ligands in order to study the magnetic interactions between the two metal centers; and secondly, to identify reactions and characterize the products whereby pre-formed iron oxide clusters undergo aggregation reactions to produce higher nuclearity products. The tetradentate ligands investigated were a bis-(beta-diketone) ligand L and a bis-bpy ligand L'. The reactions involving L and Fe(III) reagents produced complexes with a triple

  5. Unsaturated platinum-rhenium cluster complexes. Synthesis, structures and reactivity.

    PubMed

    Adams, Richard D; Captain, Burjor; Smith, Mark D; Beddie, Chad; Hall, Michael B

    2007-05-09

    Two new compounds PtRe3(CO)12(PBut3)(micro-H)3, 9, and PtRe2(CO)9(PBut3)(micro-H)2, 10, were obtained from the reaction of Pt(PBut3)2 with Re3(CO)12(micro-H3), 8, at room temperature. Compound 9 contains a butterfly cluster of four metals formed by the insertion of the platinum atom from a Pt(PBut3) group into one of the hydride-bridged metal-metal bonds of 8. The three hydrido ligands are bridging ligands across each of three new Pt-Re bonds. Compound 10 contains a triangular PtRe2 cluster with two hydrido ligands; one bridges a Pt-Re bond, and the other bridges the Re-Re bond. The new compound Pt2Re2(CO)7(PBut3)2(micro-H)2, 11, was obtained from the reaction of 8 with Pt(PBut3)2 in hexane at reflux. Compound 11 was also obtained from 10 by reaction with an additional quantity of Pt(PBut3)2. Compound 11 contains a tetrahedral cluster of four metal atoms with two dynamically active hydrido ligands. A CO ligand on one of the two platinum atoms also exchanges between the two platinum atoms rapidly on the NMR time scale. Compound 11 is electronically unsaturated and was found to add hydrogen at room temperature to form the tetrahydrido cluster complex, Pt2Re2(CO)7(PBut3)2(micro-H)4, 12. Compound 12 has a structure similar to 11 but contains one triply bridging hydrido ligand, two edge bridging hydrido ligands, and one terminal hydrido ligand on one of the two platinum atoms. A kinetic isotope effect D/H of 1.5(1) was determined for the addition of H2 to 11. Hydrogen can be eliminated from 12 by heating to 97 degrees C or by the application of UV-vis irradiation at room temperature. Compound 12 adds CO at room temperature to yield the complex Pt2Re2(CO)8(PBut3)2(micro-H)4, 13, which contains a planar cluster of four metal atoms with a Pt-Pt bond and four edge bridging hydrido ligands. Compounds 11 and 12 react with Pt(PBut3)2 to yield the known five metal cluster complexes Pt3Re2(CO)6(PBut3)3(micro-H)2, 14, and Pt3Re2(CO)6(PBut3)3(micro-H)4, 15, respectively. Density

  6. Analysis of cluster explosive synchronization in complex networks.

    PubMed

    Ji, Peng; Peron, Thomas K D M; Rodrigues, Francisco A; Kurths, Jürgen

    2014-12-01

    Correlations between intrinsic dynamics and local topology have become a new trend in the study of synchronization in complex networks. In this paper, we investigate the influence of topology on the dynamics of networks made up of second-order Kuramoto oscillators. In particular, based on mean-field calculations, we provide a detailed investigation of cluster explosive synchronization (CES) [Phys. Rev. Lett. 110, 218701 (2013)] in scale-free networks as a function of several topological properties. Moreover, we investigate the robustness of discontinuous transitions by including an additional quenched disorder, and we show that the phase coherence decreases with increasing strength of the quenched disorder. These results complement the previous findings regarding CES and also fundamentally deepen the understanding of the interplay between topology and dynamics under the constraint of correlating natural frequencies and local structure.

  7. A machine learning approach for ranking clusters of docked protein-protein complexes by pairwise cluster comparison.

    PubMed

    Pfeiffenberger, Erik; Chaleil, Raphael A G; Moal, Iain H; Bates, Paul A

    2017-03-01

    Reliable identification of near-native poses of docked protein-protein complexes is still an unsolved problem. The intrinsic heterogeneity of protein-protein interactions is challenging for traditional biophysical or knowledge based potentials and the identification of many false positive binding sites is not unusual. Often, ranking protocols are based on initial clustering of docked poses followed by the application of an energy function to rank each cluster according to its lowest energy member. Here, we present an approach of cluster ranking based not only on one molecular descriptor (e.g., an energy function) but also employing a large number of descriptors that are integrated in a machine learning model, whereby, an extremely randomized tree classifier based on 109 molecular descriptors is trained. The protocol is based on first locally enriching clusters with additional poses, the clusters are then characterized using features describing the distribution of molecular descriptors within the cluster, which are combined into a pairwise cluster comparison model to discriminate near-native from incorrect clusters. The results show that our approach is able to identify clusters containing near-native protein-protein complexes. In addition, we present an analysis of the descriptors with respect to their power to discriminate near native from incorrect clusters and how data transformations and recursive feature elimination can improve the ranking performance. Proteins 2017; 85:528-543. © 2016 Wiley Periodicals, Inc.

  8. ClusterViSu, a method for clustering of protein complexes by Voronoi tessellation in super-resolution microscopy

    PubMed Central

    Andronov, Leonid; Orlov, Igor; Lutz, Yves; Vonesch, Jean-Luc; Klaholz, Bruno P.

    2016-01-01

    Super-resolution microscopy (PALM, STORM etc.) provides a plethora of fluorescent signals in dense cellular environments which can be difficult to interpret. Here we describe ClusterViSu, a method for image reconstruction, visualization and quantification of labelled protein clusters, based on Voronoi tessellation of the individual fluorescence events. The general applicability of this clustering approach for the segmentation of super-resolution microscopy data, including for co-localization, is illustrated on a series of important biological objects such as chromatin complexes, RNA polymerase, nuclear pore complexes and microtubules. PMID:27068792

  9. Synthesis, characterization, and structure of reduced tungsten chalcogenide cluster complexes

    SciTech Connect

    Xiaobing, Xie

    1997-10-17

    Over the previous twenty years, ternary molybdenum chalcogenides of the general formula MxMo6Y8 (M = ternary metal cation; Y = chalcogenide), known as Chevrel phases, have been extensively studied. Many of these compounds have been found to have superconductivity, catalytic activity and ionic conductivity. The rich chemistry of the Chevrel phases raises considerable interest in finding the tungsten analogues of these phases. However, no such analogue has ever been synthesized, although the Chevrel phases are usually prepared directly from elements at high temperatures above 1000{degrees}C. The absence of the tungsten analogues may be caused by their thermodynamic instability at such high temperatures. Thus it might be necessary to avoid high-temperature synthetic procedures in order to establish the ternary and binary tungsten chalcogenides. A major focus of the McCarley research group has been on the preparation of M6Y8L6 (M = Mo, W; Y = S, Se, Te) cluster complexes as low temperature pathways to the Chevrel phases.

  10. Effect of mitochondrial complex I inhibition on Fe-S cluster protein activity

    SciTech Connect

    Mena, Natalia P.; Bulteau, Anne Laure; Salazar, Julio; Hirsch, Etienne C.; Nunez, Marco T.

    2011-06-03

    Highlights: {yields} Mitochondrial complex I inhibition resulted in decreased activity of Fe-S containing enzymes mitochondrial aconitase and cytoplasmic aconitase and xanthine oxidase. {yields} Complex I inhibition resulted in the loss of Fe-S clusters in cytoplasmic aconitase and of glutamine phosphoribosyl pyrophosphate amidotransferase. {yields} Consistent with loss of cytoplasmic aconitase activity, an increase in iron regulatory protein 1 activity was found. {yields} Complex I inhibition resulted in an increase in the labile cytoplasmic iron pool. -- Abstract: Iron-sulfur (Fe-S) clusters are small inorganic cofactors formed by tetrahedral coordination of iron atoms with sulfur groups. Present in numerous proteins, these clusters are involved in key biological processes such as electron transfer, metabolic and regulatory processes, DNA synthesis and repair and protein structure stabilization. Fe-S clusters are synthesized mainly in the mitochondrion, where they are directly incorporated into mitochondrial Fe-S cluster-containing proteins or exported for cytoplasmic and nuclear cluster-protein assembly. In this study, we tested the hypothesis that inhibition of mitochondrial complex I by rotenone decreases Fe-S cluster synthesis and cluster content and activity of Fe-S cluster-containing enzymes. Inhibition of complex I resulted in decreased activity of three Fe-S cluster-containing enzymes: mitochondrial and cytosolic aconitases and xanthine oxidase. In addition, the Fe-S cluster content of glutamine phosphoribosyl pyrophosphate amidotransferase and mitochondrial aconitase was dramatically decreased. The reduction in cytosolic aconitase activity was associated with an increase in iron regulatory protein (IRP) mRNA binding activity and with an increase in the cytoplasmic labile iron pool. Since IRP activity post-transcriptionally regulates the expression of iron import proteins, Fe-S cluster inhibition may result in a false iron deficiency signal. Given that

  11. The complex star cluster system of NGC 1316 (Fornax A)

    NASA Astrophysics Data System (ADS)

    Sesto, Leandro A.; Faifer, Favio R.; Forte, Juan C.

    2016-10-01

    This paper presents Gemini-gri' high-quality photometry for cluster candidates in the field of NGC 1316 (Fornax A) as part of a study that also includes GMOS spectroscopy. A preliminary discussion of the photometric data indicates the presence of four stellar cluster populations with distinctive features in terms of age, chemical abundance and spatial distribution. Two of them seem to be the usually old (metal poor and metal rich) populations typically found in elliptical galaxies. In turn, an intermediate-age (5 Gyr) globular cluster population is the dominant component of the sample (as reported by previous papers). We also find a younger cluster population with a tentative age of ≈ 1 Gyr.

  12. Reconstructing Histories of Complex Gene Clusters on a Phylogeny

    NASA Astrophysics Data System (ADS)

    Vinař, Tomáš; Brejová, Broňa; Song, Giltae; Siepel, Adam

    Clusters of genes that have evolved by repeated segmental duplication present difficult challenges throughout genomic analysis, from sequence assembly to functional analysis. These clusters are one of the major sources of evolutionary innovation, and they are linked to multiple diseases, including HIV and a variety of cancers. Understanding their evolutionary histories is a key to the application of comparative genomics methods in these regions of the genome. We propose a probabilistic model of gene cluster evolution on a phylogeny, and an MCMC algorithm for reconstruction of duplication histories from genomic sequences in multiple species. Several projects are underway to obtain high quality BAC-based assemblies of duplicated clusters in multiple species, and we anticipate use of our methods in their analysis. Supplementary materials are located at http://compbio.fmph.uniba.sk/suppl/09recombcg/

  13. A Near-infrared Survey of the Rosette Complex: Clues of Early Cluster Evolution

    NASA Astrophysics Data System (ADS)

    Román-Zúñiga, Carlos G.; Lada, Elizabeth A.; Ferreira, Bruno

    2008-05-01

    The majority of stars in our galaxy are born in embedded clusters, which can be considered the fundamental units of star formation. We have recently surveyed the star forming content of the Rosette Complex using FLAMINGOS in order to investigate the properties of its embedded clusters. We discuss the results of our near-infrared imaging survey. In particular, we on the first evidence for the early evolution and expansion of the embedded clusters. In addition we present data suggesting a temporal sequence of cluster formation across the cloud and discuss the influence of the HII region on the star forming history of the Rosette.

  14. The multitude of iron-sulfur clusters in respiratory complex I.

    PubMed

    Gnandt, Emmanuel; Dörner, Katerina; Strampraad, Marc F J; de Vries, Simon; Friedrich, Thorsten

    2016-08-01

    Respiratory complex I couples the electron transfer from NADH to ubiquinone with the translocation of protons across the membrane. Complex I contains one non-covalently bound flavin mononucleotide and, depending on the species, up to ten iron-sulfur (Fe/S) clusters as cofactors. The reason for the presence of the multitude of Fe/S clusters in complex I remained enigmatic for a long time. The question was partly answered by investigations on the evolution of the complex revealing the stepwise construction of the electron transfer domain from several modules. Extension of the ancestral to the modern electron input domain was associated with the acquisition of several Fe/S-proteins. The X-ray structure of the complex showed that the NADH oxidation-site is connected with the quinone-reduction site by a chain of seven Fe/S-clusters. Fast enzyme kinetics revealed that this chain of Fe/S-clusters is used to regulate electron-tunneling rates within the complex. A possible function of the off-pathway cluster N1a is discussed. This article is part of a Special Issue entitled 'EBEC 2016: 19th European Bioenergetics Conference, Riva del Garda, Italy, July 2-6, 2016', edited by Prof. Paolo Bernardi.

  15. Link-Prediction Enhanced Consensus Clustering for Complex Networks.

    PubMed

    Burgess, Matthew; Adar, Eytan; Cafarella, Michael

    2016-01-01

    Many real networks that are collected or inferred from data are incomplete due to missing edges. Missing edges can be inherent to the dataset (Facebook friend links will never be complete) or the result of sampling (one may only have access to a portion of the data). The consequence is that downstream analyses that "consume" the network will often yield less accurate results than if the edges were complete. Community detection algorithms, in particular, often suffer when critical intra-community edges are missing. We propose a novel consensus clustering algorithm to enhance community detection on incomplete networks. Our framework utilizes existing community detection algorithms that process networks imputed by our link prediction based sampling algorithm and merges their multiple partitions into a final consensus output. On average our method boosts performance of existing algorithms by 7% on artificial data and 17% on ego networks collected from Facebook.

  16. Experimental studies of complex crater formation under cluster implantation of solids

    NASA Astrophysics Data System (ADS)

    Prasalovich, S.; Popok, V.; Persson, P.; Campbell, E. E. B.

    2005-10-01

    The results of a systematic study of surface defect formation after energetic Arn+ (n = 12, 22, 32, 54) and Xen+ (n = 4, 16) cluster ion implantation into silicon and sapphire are presented. Implantation energies vary from 3 to 18 keV/ion. Two cases of comparative studies are carried out: the same cluster species are implanted into two different substrates, i.e. Arn+ cluster ions into silicon and sapphire and two different cluster species Arn+ and Xen+ are implanted into the same kind of substrate (silicon). Atomic force, scanning electron and transmission electron microscopies (AFM, SEM and TEM) are used to study the implanted samples. The analysis reveals the formation of two types of surface erosion defects: simple and complex (with centrally positioned hillock) craters. It is found that the ratio of simple to complex crater formation as well as the hillock dimensions depend strongly on the cluster species, size and impact energy as well as on the type of substrate material. Qualitative models describing the two comparative cases of cluster implantation, the case of different cluster species and the case of different substrate materials, are proposed.

  17. Membrane skeleton orchestrates the platelet glycoprotein (GP) Ib-IX complex clustering and signaling.

    PubMed

    Shang, Dan; Zhang, Zuping; Wang, Qian; Ran, Yali; Shaw, Tanner S; Van, John N; Peng, Yuandong

    2016-10-01

    Platelet glycoprotein Ib-IX complex is affixed to the membrane skeleton through interaction with actin binding protein 280 (ABP-280). We find that removal of the ABP-280 binding sites in GP Ibα cytoplasmic tail has little impact on the complex clustering induced by antibody crosslinking. However, large truncation of the GP Ibα cytoplasmic tail allows the formation of larger patches of the complex, suggesting that an ABP-280 independent force may exist. Besides, we observe that the signaling upon GP Ib-IX clustering is elicited in both membrane lipid domain dependent and independent manner, a choice that relies on how the membrane skeleton interacts with the complex. Our findings suggest a more complex mechanism for how the membrane skeleton regulates the GP Ib-IX function. © 2016 IUBMB Life, 68(10):823-829, 2016.

  18. Directed clustering coefficient as a measure of systemic risk in complex banking networks

    NASA Astrophysics Data System (ADS)

    Tabak, Benjamin M.; Takami, Marcelo; Rocha, Jadson M. C.; Cajueiro, Daniel O.; Souza, Sergio R. S.

    2014-01-01

    Recent literature has focused on the study of systemic risk in complex networks. It is clear now, after the crisis of 2008, that the aggregate behavior of the interaction among agents is not straightforward and it is very difficult to predict. Contributing to this debate, this paper shows that the directed clustering coefficient may be used as a measure of systemic risk in complex networks. Furthermore, using data from the Brazilian interbank network, we show that the directed clustering coefficient is negatively correlated with domestic interest rates.

  19. Cluster formation by allelomimesis in real-world complex adaptive systems

    NASA Astrophysics Data System (ADS)

    Juanico, Dranreb Earl; Monterola, Christopher; Saloma, Caesar

    2005-04-01

    Animal and human clusters are complex adaptive systems and many organize in cluster sizes s that obey the frequency distribution D(s)∝s-τ . The exponent τ describes the relative abundance of the cluster sizes in a given system. Data analyses reveal that real-world clusters exhibit a broad spectrum of τ values, 0.7 (tuna fish schools) ⩽τ⩽4.61 (T4 bacteriophage gene family sizes). Allelomimesis is proposed as an underlying mechanism for adaptation that explains the observed broad τ spectrum. Allelomimesis is the tendency of an individual to imitate the actions of others and two cluster systems have different τ values when their component agents display unequal degrees of allelomimetic tendencies. Cluster formation by allelomimesis is shown to be of three general types: namely, blind copying, information-use copying, and noncopying. Allelomimetic adaptation also reveals that the most stable cluster size is formed by three strongly allelomimetic individuals. Our finding is consistent with available field data taken from killer whales and marmots.

  20. Analysis of the Tribolium homeotic complex: insights into mechanisms constraining insect Hox clusters

    PubMed Central

    Ronshaugen, Matthew; Cande, Jessica; He, JianPing; Beeman, Richard W.; Levine, Michael; Brown, Susan J.; Denell, Robin E.

    2008-01-01

    The remarkable conservation of Hox clusters is an accepted but little understood principle of biology. Some organizational constraints have been identified for vertebrate Hox clusters, but most of these are thought to be recent innovations that may not apply to other organisms. Ironically, many model organisms have disrupted Hox clusters and may not be well-suited for studies of structural constraints. In contrast, the red flour beetle, Tribolium castaneum, which has a long history in Hox gene research, is thought to have a more ancestral-type Hox cluster organization. Here, we demonstrate that the Tribolium homeotic complex (HOMC) is indeed intact, with the individual Hox genes in the expected colinear arrangement and transcribed from the same strand. There is no evidence that the cluster has been invaded by non-Hox protein-coding genes, although expressed sequence tag and genome tiling data suggest that noncoding transcripts are prevalent. Finally, our analysis of several mutations affecting the Tribolium HOMC suggests that intermingling of enhancer elements with neighboring transcription units may constrain the structure of at least one region of the Tribolium cluster. This work lays a foundation for future studies of the Tribolium HOMC that may provide insights into the reasons for Hox cluster conservation. PMID:18392875

  1. Ant colony clustering with fitness perception and pheromone diffusion for community detection in complex networks

    NASA Astrophysics Data System (ADS)

    Ji, Junzhong; Song, Xiangjing; Liu, Chunnian; Zhang, Xiuzhen

    2013-08-01

    Community structure detection in complex networks has been intensively investigated in recent years. In this paper, we propose an adaptive approach based on ant colony clustering to discover communities in a complex network. The focus of the method is the clustering process of an ant colony in a virtual grid, where each ant represents a node in the complex network. During the ant colony search, the method uses a new fitness function to percept local environment and employs a pheromone diffusion model as a global information feedback mechanism to realize information exchange among ants. A significant advantage of our method is that the locations in the grid environment and the connections of the complex network structure are simultaneously taken into account in ants moving. Experimental results on computer-generated and real-world networks show the capability of our method to successfully detect community structures.

  2. Label propagation algorithm based on edge clustering coefficient for community detection in complex networks

    NASA Astrophysics Data System (ADS)

    Zhang, Xian-Kun; Tian, Xue; Li, Ya-Nan; Song, Chen

    2014-08-01

    The label propagation algorithm (LPA) is a graph-based semi-supervised learning algorithm, which can predict the information of unlabeled nodes by a few of labeled nodes. It is a community detection method in the field of complex networks. This algorithm is easy to implement with low complexity and the effect is remarkable. It is widely applied in various fields. However, the randomness of the label propagation leads to the poor robustness of the algorithm, and the classification result is unstable. This paper proposes a LPA based on edge clustering coefficient. The node in the network selects a neighbor node whose edge clustering coefficient is the highest to update the label of node rather than a random neighbor node, so that we can effectively restrain the random spread of the label. The experimental results show that the LPA based on edge clustering coefficient has made improvement in the stability and accuracy of the algorithm.

  3. Neptunium(vi) chain and neptunium(vi/v) mixed valence cluster complexes.

    PubMed

    Cornet, Stéphanie M; Häller, L Jonas L; Sarsfield, Mark J; Collison, David; Helliwell, Madeleine; May, Iain; Kaltsoyannis, Nikolas

    2009-02-28

    The synthesis of [Np(VI)O(2)Cl(2)(thf)](n) offers the potential for more detailed exploration of neptunyl(vi) chemistry, while the synthesis of the mixed valence cluster complex [{Np(VI)O(2)Cl(2)}{Np(V)O(2)Cl(thf)(3)}(2)] allows molecular neptunyl(v) 'cation-cation' interactions to be probed.

  4. Adult Speakers' Tongue-Palate Contact Patterns for Bilabial Stops within Complex Clusters

    ERIC Educational Resources Information Center

    Zharkova, Natalia; Schaeffler, Sonja; Gibbon, Fiona E.

    2009-01-01

    Previous studies using Electropalatography (EPG) have shown that individuals with speech disorders sometimes produce articulation errors that affect bilabial targets, but currently there is limited normative data available. In this study, EPG and acoustic data were recorded during complex word final sps clusters spoken by 20 normal adults. A total…

  5. Prospects of molybdenum and rhenium octahedral cluster complexes as X-ray contrast agents.

    PubMed

    Krasilnikova, Anna A; Shestopalov, Michael A; Brylev, Konstantin A; Kirilova, Irina A; Khripko, Olga P; Zubareva, Kristina E; Khripko, Yuri I; Podorognaya, Valentina T; Shestopalova, Lidiya V; Fedorov, Vladimir E; Mironov, Yuri V

    2015-03-01

    Investigation of new X-ray contrast media for radiography is an important field of science since discovering of X-rays in 1895. Despite the wide diversity of available X-ray contrast media the toxicity, especially nephrotoxicity, is still a big problem to be solved. The octahedral metal-cluster complexes of the general formula [{M6Q8}L6] can be considered as quite promising candidates for the role of new radiocontrast media due to the high local concentration of heavy elements, high tuning ability of ligand environment and low toxicity. To exemplify this, the X-ray computed tomography experiments for the first time were carried out on some octahedral cluster complexes of molybdenum and rhenium. Based on the obtained data it was proposed to investigate the toxicological proprieties of cluster complex Na2H8[{Re6Se8}(P(CH2CH2CONH2)(CH2CH2COO)2)6]. Observed low cytotoxic and acute toxic effects along with rapid renal excretion of the cluster complex evidence its perspective as an X-ray contrast media for radiography.

  6. The Geometric Cluster Algorithm: Rejection-Free Monte Carlo Simulation of Complex Fluids

    NASA Astrophysics Data System (ADS)

    Luijten, Erik

    2005-03-01

    The study of complex fluids is an area of intense research activity, in which exciting and counter-intuitive behavior continue to be uncovered. Ironically, one of the very factors responsible for such interesting properties, namely the presence of multiple relevant time and length scales, often greatly complicates accurate theoretical calculations and computer simulations that could explain the observations. We have recently developed a new Monte Carlo simulation methodootnotetextJ. Liu and E. Luijten, Phys. Rev. Lett.92, 035504 (2004); see also Physics Today, March 2004, pp. 25--27. that overcomes this problem for several classes of complex fluids. Our approach can accelerate simulations by orders of magnitude by introducing nonlocal, collective moves of the constituents. Strikingly, these cluster Monte Carlo moves are proposed in such a manner that the algorithm is rejection-free. The identification of the clusters is based upon geometric symmetries and can be considered as the off-latice generalization of the widely-used Swendsen--Wang and Wolff algorithms for lattice spin models. While phrased originally for complex fluids that are governed by the Boltzmann distribution, the geometric cluster algorithm can be used to efficiently sample configurations from an arbitrary underlying distribution function and may thus be applied in a variety of other areas. In addition, I will briefly discuss various extensions of the original algorithm, including methods to influence the size of the clusters that are generated and ways to introduce density fluctuations.

  7. Complex Network Clustering by a Multi-objective Evolutionary Algorithm Based on Decomposition and Membrane Structure

    NASA Astrophysics Data System (ADS)

    Ju, Ying; Zhang, Songming; Ding, Ningxiang; Zeng, Xiangxiang; Zhang, Xingyi

    2016-09-01

    The field of complex network clustering is gaining considerable attention in recent years. In this study, a multi-objective evolutionary algorithm based on membranes is proposed to solve the network clustering problem. Population are divided into different membrane structures on average. The evolutionary algorithm is carried out in the membrane structures. The population are eliminated by the vector of membranes. In the proposed method, two evaluation objectives termed as Kernel J-means and Ratio Cut are to be minimized. Extensive experimental studies comparison with state-of-the-art algorithms proves that the proposed algorithm is effective and promising.

  8. Complex Network Clustering by a Multi-objective Evolutionary Algorithm Based on Decomposition and Membrane Structure

    PubMed Central

    Ju, Ying; Zhang, Songming; Ding, Ningxiang; Zeng, Xiangxiang; Zhang, Xingyi

    2016-01-01

    The field of complex network clustering is gaining considerable attention in recent years. In this study, a multi-objective evolutionary algorithm based on membranes is proposed to solve the network clustering problem. Population are divided into different membrane structures on average. The evolutionary algorithm is carried out in the membrane structures. The population are eliminated by the vector of membranes. In the proposed method, two evaluation objectives termed as Kernel J-means and Ratio Cut are to be minimized. Extensive experimental studies comparison with state-of-the-art algorithms proves that the proposed algorithm is effective and promising. PMID:27670156

  9. Complex nanoscale cage clusters built from uranyl polyhedra and phosphate tetrahedra

    SciTech Connect

    Unruh, Daniel K.; Ling, Jie; Qiu, Jie; Pressprich, Laura; Baranay, Melissa; Ward, Matthew; Burns, Peter C.

    2011-06-20

    Five cage clusters that self-assemble in alkaline aqueous solution have been isolated and characterized. Each is built from uranyl hexagonal bipyramids with two or three equatorial edges occupied by peroxide, and three also contain phosphate tetrahedra. These clusters contain 30 uranyl polyhedra; 30 uranyl polyhedra and six pyrophosphate groups; 30 uranyl polyhedra, 12 pyrophosphate groups, and one phosphate tetrahedron; 42 uranyl polyhedra; and 40 uranyl polyhedra and three pyrophosphate groups. These clusters present complex topologies as well as a range of compositions, sizes, and charges. Two adopt fullerene topologies, and the others contain combinations of topological squares, pentagons, and hexagons. An analysis of possible topologies further indicates that higher-symmetry topologies are favored.

  10. Adaptive fuzzy leader clustering of complex data sets in pattern recognition

    NASA Technical Reports Server (NTRS)

    Newton, Scott C.; Pemmaraju, Surya; Mitra, Sunanda

    1992-01-01

    A modular, unsupervised neural network architecture for clustering and classification of complex data sets is presented. The adaptive fuzzy leader clustering (AFLC) architecture is a hybrid neural-fuzzy system that learns on-line in a stable and efficient manner. The initial classification is performed in two stages: a simple competitive stage and a distance metric comparison stage. The cluster prototypes are then incrementally updated by relocating the centroid positions from fuzzy C-means system equations for the centroids and the membership values. The AFLC algorithm is applied to the Anderson Iris data and laser-luminescent fingerprint image data. It is concluded that the AFLC algorithm successfully classifies features extracted from real data, discrete or continuous.

  11. H ∞ Cluster Synchronization for a Class of Neutral Complex Dynamical Networks with Markovian Switching

    PubMed Central

    2014-01-01

    H ∞ cluster synchronization problem for a class of neutral complex dynamical networks (NCDNs) with Markovian switching is investigated in this paper. Both the retarded and neutral delays are considered to be interval mode dependent and time varying. The concept of H ∞ cluster synchronization is proposed to quantify the attenuation level of synchronization error dynamics against the exogenous disturbance of the NCDNs. Based on a novel Lyapunov functional, by employing some integral inequalities and the nature of convex combination, mode delay-range-dependent H ∞ cluster synchronization criteria are derived in the form of linear matrix inequalities which depend not only on the disturbance attenuation but also on the initial values of the NCDNs. Finally, numerical examples are given to demonstrate the feasibility and effectiveness of the proposed theoretical results. PMID:24892088

  12. Studying the Effect of a Composition of the Cluster Core in High-Radiopacity Cluster Complexes of Rhenium on Their Acute Toxicity In Vivo.

    PubMed

    Pozmogova, T N; Krasil'nikova, A A; Ivanov, A A; Shestopalov, M A; Gyrylova, S N; Shestopalova, L V; Shestopaloiv, A M; Shkurupy, V A

    2016-05-01

    An in vivo study was performed to evaluate the dependence of acute toxicity of high-radiopacity and luminescent octahedral cluster complexes of rhenium after intravenous injection on a composition of the cluster core. Changes in mouse body weight, water and food consumption, degree of intoxication, and morphological changes in the visceral organs were studied after intravenous injection of the following cluster complexes with various internal ligands (S, Se, or Te): Na4[{Re 6 Te 8 }(CN)6], Na4[{Re 6 Se 8 }(CN)6], and Na4[{Re 6 S 8 }(CN)6]. The Na4[{Re 6 S 8 } (CN)6] cluster complex was shown to be the safest for animals.

  13. Biodistribution of rhenium cluster complex K₄[Re6S8(CN)6] in the body of laboratory rats.

    PubMed

    Brylev, K A; Shestopalov, M A; Khripko, O P; Trunova, V A; Zvereva, V V; Wang, C C; Mironov, Yu V; Fedorov, V E

    2013-10-01

    We studied the biodistribution of luminescent octahedral rhenium cluster complex K4[Re6S8(CN)6], a promising agent for photodynamic therapy. It was shown that rhenium complex [Re6S8(CN)6](4-)is mainly accumulated in the liver, the central organ of metabolism, and can be excreted by the kidneys. The cluster complex was also accumulated in the spleen in significant amount, which makes it a promising agent for creation of preparations for diagnostics and treatment of lymphoproliferative disorders. The mean lethal dose of the cluster complex was 0.38 g/kg.

  14. Minimal Model of Quantum Kinetic Clusters for the Energy-Transfer Network of a Light-Harvesting Protein Complex.

    PubMed

    Wu, Jianlan; Tang, Zhoufei; Gong, Zhihao; Cao, Jianshu; Mukamel, Shaul

    2015-04-02

    The energy absorbed in a light-harvesting protein complex is often transferred collectively through aggregated chromophore clusters. For population evolution of chromophores, the time-integrated effective rate matrix allows us to construct quantum kinetic clusters quantitatively and determine the reduced cluster-cluster transfer rates systematically, thus defining a minimal model of energy-transfer kinetics. For Fenna-Matthews-Olson (FMO) and light-havrvesting complex II (LCHII) monomers, quantum Markovian kinetics of clusters can accurately reproduce the overall energy-transfer process in the long-time scale. The dominant energy-transfer pathways are identified in the picture of aggregated clusters. The chromophores distributed extensively in various clusters can assist a fast and long-range energy transfer.

  15. Complete characterization of the stability of cluster synchronization in complex dynamical networks

    PubMed Central

    Sorrentino, Francesco; Pecora, Louis M.; Hagerstrom, Aaron M.; Murphy, Thomas E.; Roy, Rajarshi

    2016-01-01

    Synchronization is an important and prevalent phenomenon in natural and engineered systems. In many dynamical networks, the coupling is balanced or adjusted to admit global synchronization, a condition called Laplacian coupling. Many networks exhibit incomplete synchronization, where two or more clusters of synchronization persist, and computational group theory has recently proved to be valuable in discovering these cluster states based on the topology of the network. In the important case of Laplacian coupling, additional synchronization patterns can exist that would not be predicted from the group theory analysis alone. Understanding how and when clusters form, merge, and persist is essential for understanding collective dynamics, synchronization, and failure mechanisms of complex networks such as electric power grids, distributed control networks, and autonomous swarming vehicles. We describe a method to find and analyze all of the possible cluster synchronization patterns in a Laplacian-coupled network, by applying methods of computational group theory to dynamically equivalent networks. We present a general technique to evaluate the stability of each of the dynamically valid cluster synchronization patterns. Our results are validated in an optoelectronic experiment on a five-node network that confirms the synchronization patterns predicted by the theory. PMID:27152349

  16. Complete characterization of the stability of cluster synchronization in complex dynamical networks.

    PubMed

    Sorrentino, Francesco; Pecora, Louis M; Hagerstrom, Aaron M; Murphy, Thomas E; Roy, Rajarshi

    2016-04-01

    Synchronization is an important and prevalent phenomenon in natural and engineered systems. In many dynamical networks, the coupling is balanced or adjusted to admit global synchronization, a condition called Laplacian coupling. Many networks exhibit incomplete synchronization, where two or more clusters of synchronization persist, and computational group theory has recently proved to be valuable in discovering these cluster states based on the topology of the network. In the important case of Laplacian coupling, additional synchronization patterns can exist that would not be predicted from the group theory analysis alone. Understanding how and when clusters form, merge, and persist is essential for understanding collective dynamics, synchronization, and failure mechanisms of complex networks such as electric power grids, distributed control networks, and autonomous swarming vehicles. We describe a method to find and analyze all of the possible cluster synchronization patterns in a Laplacian-coupled network, by applying methods of computational group theory to dynamically equivalent networks. We present a general technique to evaluate the stability of each of the dynamically valid cluster synchronization patterns. Our results are validated in an optoelectronic experiment on a five-node network that confirms the synchronization patterns predicted by the theory.

  17. Clustering of protein families into functional subtypes using Relative Complexity Measure with reduced amino acid alphabets

    PubMed Central

    2010-01-01

    Background Phylogenetic analysis can be used to divide a protein family into subfamilies in the absence of experimental information. Most phylogenetic analysis methods utilize multiple alignment of sequences and are based on an evolutionary model. However, multiple alignment is not an automated procedure and requires human intervention to maintain alignment integrity and to produce phylogenies consistent with the functional splits in underlying sequences. To address this problem, we propose to use the alignment-free Relative Complexity Measure (RCM) combined with reduced amino acid alphabets to cluster protein families into functional subtypes purely on sequence criteria. Comparison with an alignment-based approach was also carried out to test the quality of the clustering. Results We demonstrate the robustness of RCM with reduced alphabets in clustering of protein sequences into families in a simulated dataset and seven well-characterized protein datasets. On protein datasets, crotonases, mandelate racemases, nucleotidyl cyclases and glycoside hydrolase family 2 were clustered into subfamilies with 100% accuracy whereas acyl transferase domains, haloacid dehalogenases, and vicinal oxygen chelates could be assigned to subfamilies with 97.2%, 96.9% and 92.2% accuracies, respectively. Conclusions The overall combination of methods in this paper is useful for clustering protein families into subtypes based on solely protein sequence information. The method is also flexible and computationally fast because it does not require multiple alignment of sequences. PMID:20718947

  18. Bimetallic octahedral ruthenium-nickel carbido cluster complexes. Synthesis and structural characterization.

    PubMed

    Saha, Sumit; Zhu, Lei; Captain, Burjor

    2013-03-04

    The reaction of Ru5(CO)15(μ5-C) with Ni(COD)2 in acetonitrile at 80 °C affords the bimetallic octahedral ruthenium-nickel cluster complex Ru5Ni(NCMe)(CO)15(μ6-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH3 to yield Ru5Ni(CO)16(μ6-C), 4, and Ru5Ni(NH3)(CO)15(μ6-C), 5, respectively. Photolysis of compound 3 in benzene and toluene solvent yielded the η(6)-coordinated benzene and toluene Ru5Ni carbido cluster complexes Ru5Ni(CO)13(η(6)-C6H6)(μ6-C), 6, and Ru5Ni(CO)13(η(6)-C7H8)(μ6-C), 7, respectively. All five new compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  19. Hexaazide octahedral molybdenum cluster complexes: Synthesis, properties and the evidence of hydrolysis

    NASA Astrophysics Data System (ADS)

    Vorotnikov, Yuri A.; Efremova, Olga A.; Novozhilov, Igor N.; Yanshole, Vadim V.; Kuratieva, Natalia V.; Brylev, Konstantin A.; Kitamura, Noboru; Mironov, Yuri V.; Shestopalov, Michael A.

    2017-04-01

    This article reports the synthesis, crystal structure of new molybdenum hexaazide cluster complex (nBu4N)2[{Mo6I8}(N3)6] (3) and comparison of its photophysical and electrochemical properties to those of earlier reported analogues (nBu4N)2[{Mo6X8}(N3)6] (X = Cl, Br). Additionally, the dimerisation of 3 as a result of hydrolysis was revealed by mass spectrometry and single crystal X-Ray diffraction. Indeed, the structurally characterised compound (nBu4N)4[({Mo6I8}(N3)5)2O] represents the first example of oxo-bridged dimer of octahedral molybdenum clusters complexes.

  20. A Transition Metal Complex (Venus Flytrap Cluster) for Radioimmunodetection and Radioimmunotherapy

    NASA Astrophysics Data System (ADS)

    Paxton, Raymond J.; Beatty, Barbara G.; Hawthorne, M. Frederick; Varadarajan, Aravamuthan; Williams, Lawrence E.; Curtis, Frederick L.; Knobler, Carolyn B.; Beatty, J. David; Shiveley, John E.

    1991-04-01

    A novel transition metal complex, Venus flytrap cluster (VFC), is described for the preparation of radiolabeled antibodies. VFC contained 57Co, which was held tightly between the faces of two covalently bridged carborane ligands by cluster bonding of the metal with appropriate ligand orbitals. Anti-carcinoembryonic antigen monoclonal antibody T84.66 was conjugated to 57Co-VFC with full retention of immunological activity. Biodistribution studies in nude mice bearing carcinoembryonic antigen-producing tumors showed excellent tumor localization of 57Co-VFC-T84.66. The accumulation of radionuclide in normal liver was low and independent of dose, which may reflect the stability of the radionuclide complex. These results presage the use of VFC systems for binding transition metals that are clinically useful for radio-immunodiagnosis and radioimmunotherapy.

  1. Molecular orbital calculations of octahedral molybdenum cluster complexes with the DV-X{alpha} method

    SciTech Connect

    Imoto, Hideo; Saito, Taro; Adachi, Hirohiko

    1995-04-26

    Discrete variational-{Chi}{alpha} molecular orbital methods were applied to octahedral cluster complexes, [Mo{sub 6}X{sub 8}-(PH{sub 3}){sub 6}](X = S and Se). This structure is of interest due to its role in superconductivity of Chevrel plates. Level energies are discussed and factors contributing to their separations are categorized. Agreement with empirical XPS data is excellent.

  2. Detecting overlapping protein complexes by rough-fuzzy clustering in protein-protein interaction networks.

    PubMed

    Wu, Hao; Gao, Lin; Dong, Jihua; Yang, Xiaofei

    2014-01-01

    In this paper, we present a novel rough-fuzzy clustering (RFC) method to detect overlapping protein complexes in protein-protein interaction (PPI) networks. RFC focuses on fuzzy relation model rather than graph model by integrating fuzzy sets and rough sets, employs the upper and lower approximations of rough sets to deal with overlapping complexes, and calculates the number of complexes automatically. Fuzzy relation between proteins is established and then transformed into fuzzy equivalence relation. Non-overlapping complexes correspond to equivalence classes satisfying certain equivalence relation. To obtain overlapping complexes, we calculate the similarity between one protein and each complex, and then determine whether the protein belongs to one or multiple complexes by computing the ratio of each similarity to maximum similarity. To validate RFC quantitatively, we test it in Gavin, Collins, Krogan and BioGRID datasets. Experiment results show that there is a good correspondence to reference complexes in MIPS and SGD databases. Then we compare RFC with several previous methods, including ClusterONE, CMC, MCL, GCE, OSLOM and CFinder. Results show the precision, sensitivity and separation are 32.4%, 42.9% and 81.9% higher than mean of the five methods in four weighted networks, and are 0.5%, 11.2% and 66.1% higher than mean of the six methods in five unweighted networks. Our method RFC works well for protein complexes detection and provides a new insight of network division, and it can also be applied to identify overlapping community structure in social networks and LFR benchmark networks.

  3. Ligation of erythrocyte CR1 induces its clustering in complex with scaffolding protein FAP-1

    PubMed Central

    Glodek, Aleksandra M.; Weaver, Gregory; Klickstein, Lloyd B.; Nicholson-Weller, Anne

    2008-01-01

    The primary identified function of complement receptor 1 (CR1/CD35) on primate erythrocytes is to bind complement-tagged inflammatory particles including microbes and immune complexes. When erythrocytes circulate through liver and spleen, sinusoidal phagocytes remove CR1-adherent particles and erythrocytes return to the circulation. This process of immune adherence clearance is important for host defense and prevention of autoimmunity. CR1 was previously described as clustered in the human erythrocyte membrane, which was thought to be necessary for binding complement-opsonized particles. In contrast, we demonstrate that on erythrocytes CR1 is not clustered, but dispersed, and able to bind complement-tagged particles. When fresh erythrocytes are solubilized by nonionic detergent, CR1 partitions to the cytoskeleton fraction. Using a PDZ-peptide array, CR1's cytoplasmic tail, which contains 2 PDZ-motifs, binds PDZ domains 2, 3, and 5 of Fas-associated phosphatase 1 (FAP-1), a scaffolding protein. We show that FAP-1, not previously recognized as an erythroid protein, is expressed on circulating erythrocytes. CR1 and FAP-1 coimmunoprecipitate, which confirms their molecular association. Disperse CR1 on erythrocytes may be advantageous for capturing immune-complexes, while ligation-induced CR1 clustering may prevent ingestion of the erythrocyte during the immune-complex transfer to the macrophages by keeping the opsonic stimulus localized thus preventing phagocyosis. PMID:18684861

  4. Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion

    SciTech Connect

    Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; Tomson, Neil C.; Anstey, Mitchell R.

    2016-02-01

    We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN)3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

  5. Voltage clustering in redox-active ligand complexes: mitigating electronic communication through choice of metal ion

    DOE PAGES

    Zarkesh, Ryan A.; Ichimura, Andrew S.; Monson, Todd C.; ...

    2016-02-01

    We used the redox-active bis(imino)acenapthene (BIAN) ligand to synthesize homoleptic aluminum, chromium, and gallium complexes of the general formula (BIAN)3M. The resulting compounds were characterized using X-ray crystallography, NMR, EPR, magnetic susceptibility and cyclic voltammetry measurements and modeled using both DFT and ab initio wavefunction calculations to compare the orbital contributions of main group elements and transition metals in ligand-based redox events. Ultimately, complexes of this type have the potential to improve the energy density and electrolyte stability of grid-scale energy storage technologies, such as redox flow batteries, through thermodynamically-clustered redox events.

  6. The Fas-FADD Death Domain Complex Structure Unravels Signalling by Receptor Clustering

    SciTech Connect

    Scott, F.; Stec, B; Pop, C; Dobaczewska, M; Lee, J; Monosov, E; Robinson, H; Salvesen, G; Schwarzenbacher, R; Riedl, S

    2009-01-01

    The death inducing signalling complex (DISC) formed by Fas receptor, FADD (Fas-associated death domain protein) and caspase 8 is a pivotal trigger of apoptosis1, 2, 3. The Fas-FADD DISC represents a receptor platform, which once assembled initiates the induction of programmed cell death. A highly oligomeric network of homotypic protein interactions comprised of the death domains of Fas and FADD is at the centre of DISC formation4, 5. Thus, characterizing the mechanistic basis for the Fas-FADD interaction is crucial for understanding DISC signalling but has remained unclear largely because of a lack of structural data. We have successfully formed and isolated the human Fas-FADD death domain complex and report the 2.7 A crystal structure. The complex shows a tetrameric arrangement of four FADD death domains bound to four Fas death domains. We show that an opening of the Fas death domain exposes the FADD binding site and simultaneously generates a Fas-Fas bridge. The result is a regulatory Fas-FADD complex bridge governed by weak protein-protein interactions revealing a model where the complex itself functions as a mechanistic switch. This switch prevents accidental DISC assembly, yet allows for highly processive DISC formation and clustering upon a sufficient stimulus. In addition to depicting a previously unknown mode of death domain interactions, these results further uncover a mechanism for receptor signalling solely by oligomerization and clustering events.

  7. The structural and bonding evolution in cysteine-gold cluster complexes.

    PubMed

    Zhao, Yaxue; Zhou, Feng; Zhou, Huchen; Su, Haibin

    2013-02-07

    The bonding characteristics in cysteine-gold cluster complexes represented by thiolate (Au(n)·Cys(S) (n = 1, 3, 5, 7)) and thiol (Au(n)·Cys(SH) (n = 2, 4, 6, 8)) is investigated by density functional theory with 6-31G(d,p) and Lanl2DZ hybrid basis sets. The complexes exhibit very different bonding characteristic between these two forms. In the Au(n)·Cys(S) complexes, the charge transfers from gold clusters to sulfur atoms. The number of S-Au bonds in the Au(n)·Cys(S) complexes evolves from one to two when n is greater than three. For n equals three, i.e. Au(3)·Cys(S), its ground state only has one S-Au bond. While the only S-Au bond in Au(1)·Cys(S) is mainly covalent, the nature of the S-Au bond in other thiolates is featured with the combination of covalent and donor-acceptor interactions. In particular, one stable isomer of Au(3)·Cys(S) with two S-Au bonds, which is 2 kcal mol(-1) higher in energy than the corresponding ground state, consists of one covalent and one donor-acceptor S-Au bond explicitly. Moreover, the localized three center two electron bonds are formed within the Au clusters, which facilitates the formation of the two S-Au bonds in Au(5)·Cys(S) and Au(7)·Cys(S) complexes. In the Au(n)·Cys(SH) complexes, the donor-acceptor interaction prevails in the Au-SH bond by transferring lone pair electrons from the sulfur atom to the adjacent gold atom. Interestingly, the orbital with much more 6s-component in Au(4)·Cys(SH) enhances the donor-acceptor bonding character, thus yields the strongest bonding among all the Au(n)·Cys(SH) complexes studied in this paper. In general, the bonding strength between gold clusters and cysteine is positively correlated with the S-Au overlap-weighted bond order, but negatively correlated with the S-Au bond length. Lastly, the covalent and donor-acceptor S-Au bond strength is computed to be 48 and 18 kcal mol(-1), respectively.

  8. [Classification and Contribution Analysis of Aromatic Clusters in Protein-Ligand Complexes].

    PubMed

    Yamasaki, Hiroyuki; Koseki, Jun; Nishibata, Yoshihiko; Hirono, Shuichi

    2016-01-01

      Intermolecular interactions are key features in the stabilization or destabilization of complexes. In particular, interactions involving aromatic rings have been extensively studied both theoretically and experimentally. Studies have shown that aromatic-aromatic interactions can be categorized by ring-ring orientation into a variety of different types, such as stacking interactions and T-shaped interactions. Because these different orientations affect stabilization, analyses of such interactions, for example ab initio molecular orbital calculations, are applied to pairs of aromatic rings, both in model systems and real systems. An important series of aromatic-aromatic interactions include those between pairs of aromatic residues in proteins. These residues have been studied computationally using both a theoretical chemistry approach and a knowledge-based analys. Protein 3D structural information is essential for knowledge-based studies of aromatic-aromatic interactions in protein-ligand complexes. Some databases filter entries from the Protein Data Bank (PDB) using criteria that make them suitable for computational approaches involving specific research targets. Lanzarotti et al. have shown that aromatic clusters in which three or more aromatic residues are in close proximity to each other are found in many protein structures, expanding pairwise aromatic-aromatic interactions. Moreover, these clusters are thought to be important in terms of protein function, structural stability and ligand recognition. Here, we show that aromatic clusters, as well as individual proteins, are found in a variety of protein-ligand complexes. As such, we anticipate that these clusters might have a significant role in ligand binding and could help in efficient ligand design.

  9. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    SciTech Connect

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-15

    Comproportionation reactions of rare-earth metal trihalides (RX{sub 3}) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ((T{sub 3}R{sub 11})X{sub 15}-type, P6{sub 3}/m), tetramers ((T{sub 4}R{sub 16})X{sub 28}(R{sub 4}) (P-43m), (T{sub 4}R{sub 16})X{sub 20} (P4{sub 2}/nnm), (T{sub 4}R{sub 16})X{sub 24}(RX{sub 3}){sub 4} (I4{sub 1}/a) and (T{sub 4}R{sub 16})X{sub 23} (C2/m) types of structure) and pentamers ((Ru{sub 5}La{sub 14}){sub 2}Br{sub 39}, Cc) of (TR{sub r}){sub n} (n=2–5) clusters. These oligomers are further enveloped by inner (X{sup i}) as well as outer (X{sup a}) halido ligands, which possess diverse functionalities and interconnect like oligomers through i–i, i–a and/or a–i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of (TR{sub 6}) octahedra via common edges are more frequent than trimers and pentamers, in which the (TR{sub r}) clusters share common faces. - Graphical abstract: Rare earth-metal cluster complexes with endohedral transition metal atoms (TR{sub 6}) may connect via common edges or faces to form dimers, trimers, tetramers and pentamers of which the tetramers are the most prolific. Packing effects and electron counts play an important role. - Highlights: • Rare-earth metal cluster complexes encapsulate transition metal atoms. • Oligomers are built via connection of octahedral clusters via common edges or faces. • Dimers through pentamers with closed structures are known. • Tetramers including a tetrahedron of endohedral atoms are the most prolific.

  10. A space-time model for carbapenemase-producing Klebsiella pneumoniae (KPC) cluster quantification in a high-complexity hospital.

    PubMed

    Abboud, C S; Monteiro, J; França, J I D; Pignatari, A C; De Souza, E E; Camargo, E C G; Monteiro, A M V; Dos Santos, R G; Kiffer, C R V

    2015-09-01

    A retrospective space-time permutation model with non-Euclidean distance criteria was applied within a high-complexity hospital setting to quantitatively explore cluster patterns of 273 patients infected with or colonized by carbapenemase-producing Klebsiella pneumoniae during 4 years. Results were compared to standard nosocomial active-surveillance methods. Two clusters were identified in the period, suggesting that space-time strategies for cluster quantification within confined environments may be useful.

  11. Isotope effects in the infrared spectra of OCS-He complexes and clusters.

    PubMed

    Abusara, Z; Borvayeh, L; Moazzen-Ahmadi, N; McKellar, A R W

    2006-10-14

    Infrared spectra of the OCS-He van der Waals complex and of OCS-He(N) clusters have been studied in the region of the OCS nu1 fundamental band using a tunable diode laser to probe a pulsed supersonic slit jet. For the complex, the spectrum of the normal isotope, 16O12C32S-4He, has been considerably extended and the 34S- and 13C-substituted forms have been recorded for the first time. The data could be analyzed satisfactorily using a conventional asymmetric rotor Hamiltonian with sextic centrifugal distortion terms. For the clusters, the 34S- and 13C-substituted forms have been observed and assigned for N = 2-7, including some transitions with higher J values than previously reported for the normal isotope, e.g., R5. The observed vibrational shifts, relative to the free OCS molecule, were very similar to those of the normal isotope, and most of the difference could be explained by simple scaling. These results constitute a subtle and precise probe of intermolecular forces and dynamical effects in a system which is of current interest for cluster studies.

  12. The impact of polyploidy on the evolution of a complex NB-LRR resistance gene cluster in soybean

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A comparative genomics approach was used to investigate the evolution of a complex NB-LRR gene cluster found in soybean (Glycine max), common bean (Phaseolus vulgaris), and other legumes. In soybean, the cluster is associated with several disease resistance (R) genes of known function including Rpg1...

  13. High resolution Raman spectroscopy of complexes and clusters in molecular beams. Performance report

    SciTech Connect

    Felker, P.M.

    1991-12-31

    The DOE-sponsored project in this laboratory has two facets. The first is the development of methods of nonlinear Raman spectroscopy for application in studies of sparse samples. The second is the application of such methods to structural and dynamical studies of species in supersonic molecular beams. The progress we have made in both of these areas is described in this paper. The report is divided into five remaining sections. The first pertains to theoretical and experimental developments in Fourier transform stimulated emission spectroscopy and Fourier transform hole-burning spectroscopy. The second deals with progress in the development of ionization-detected stimulated Raman spectroscopies (IDSRS). The third describes results from the application of IDSRS methods to studies of jet-cooled benzene clusters. The fourth describes IDSRS results from studies of hydrogen-bonded complexes containing phenols. The fifth relates to studies of carbazole-(Ar){sub n} clusters.

  14. High resolution Raman spectroscopy of complexes and clusters in molecular beams

    SciTech Connect

    Felker, P.M.

    1991-01-01

    The DOE-sponsored project in this laboratory has two facets. The first is the development of methods of nonlinear Raman spectroscopy for application in studies of sparse samples. The second is the application of such methods to structural and dynamical studies of species in supersonic molecular beams. The progress we have made in both of these areas is described in this paper. The report is divided into five remaining sections. The first pertains to theoretical and experimental developments in Fourier transform stimulated emission spectroscopy and Fourier transform hole-burning spectroscopy. The second deals with progress in the development of ionization-detected stimulated Raman spectroscopies (IDSRS). The third describes results from the application of IDSRS methods to studies of jet-cooled benzene clusters. The fourth describes IDSRS results from studies of hydrogen-bonded complexes containing phenols. The fifth relates to studies of carbazole-(Ar){sub n} clusters.

  15. Chemical Abundances in NGC 5053: A Very Metal Poor and Dynamically Complex Globular Cluster

    NASA Astrophysics Data System (ADS)

    Boberg, Owen; Friel, Eileen D.; Vesperini, Enrico

    2015-01-01

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the spherical distribution expected from GCs. These features include a ˜6° tidal stream (Lauchner et al. 2006), and a possible, but still debated, bridge-like structure between it and its nearby neighbor NGC 5024 (Chun et al. 2010). These features suggest that the evolution of these clusters has not only been greatly affected by their gravitational interaction with the Galaxy, but possibly each other. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sgr dSph stream (Law & Majewski 2010). Using the WIYN-Hydra multi-object spectrograph, we have collected high quality (S/N ˜75-90), medium-resolution spectra for red giant branch (RGB) stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of -2.46 with a standard deviation of 0.05 dex, making NGC 5053 one of the most metal poor GCs in the Milky Way. The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of Milky Way halo stars at a similar metallicity, with high alpha values and slightly depleted [Ba/Fe]. The Na and O abundances show the Na-O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the Milky Way. This does not, however, rule out NGC 5053 being a member of the Sgr dSph stream.

  16. The Talin Head Domain Reinforces Integrin-Mediated Adhesion by Promoting Adhesion Complex Stability and Clustering

    PubMed Central

    Ellis, Stephanie J.; Lostchuck, Emily; Goult, Benjamin T.; Bouaouina, Mohamed; Fairchild, Michael J.; López-Ceballos, Pablo; Calderwood, David A.; Tanentzapf, Guy

    2014-01-01

    Talin serves an essential function during integrin-mediated adhesion in linking integrins to actin via the intracellular adhesion complex. In addition, the N-terminal head domain of talin regulates the affinity of integrins for their ECM-ligands, a process known as inside-out activation. We previously showed that in Drosophila, mutating the integrin binding site in the talin head domain resulted in weakened adhesion to the ECM. Intriguingly, subsequent studies showed that canonical inside-out activation of integrin might not take place in flies. Consistent with this, a mutation in talin that specifically blocks its ability to activate mammalian integrins does not significantly impinge on talin function during fly development. Here, we describe results suggesting that the talin head domain reinforces and stabilizes the integrin adhesion complex by promoting integrin clustering distinct from its ability to support inside-out activation. Specifically, we show that an allele of talin containing a mutation that disrupts intramolecular interactions within the talin head attenuates the assembly and reinforcement of the integrin adhesion complex. Importantly, we provide evidence that this mutation blocks integrin clustering in vivo. We propose that the talin head domain is essential for regulating integrin avidity in Drosophila and that this is crucial for integrin-mediated adhesion during animal development. PMID:25393120

  17. Identifying driving gene clusters in complex diseases through critical transition theory

    NASA Astrophysics Data System (ADS)

    Wolanyk, Nathaniel; Wang, Xujing; Hessner, Martin; Gao, Shouguo; Chen, Ye; Jia, Shuang

    A novel approach of looking at the human body using critical transition theory has yielded positive results: clusters of genes that act in tandem to drive complex disease progression. This cluster of genes can be thought of as the first part of a large genetic force that pushes the body from a curable, but sick, point to an incurable diseased point through a catastrophic bifurcation. The data analyzed is time course microarray blood assay data of 7 high risk individuals for Type 1 Diabetes who progressed into a clinical onset, with an additional larger study requested to be presented at the conference. The normalized data is 25,000 genes strong, which were narrowed down based on statistical metrics, and finally a machine learning algorithm using critical transition metrics found the driving network. This approach was created to be repeatable across multiple complex diseases with only progression time course data needed so that it would be applicable to identifying when an individual is at risk of developing a complex disease. Thusly, preventative measures can be enacted, and in the longer term, offers a possible solution to prevent all Type 1 Diabetes.

  18. Photodissociation of HCl and small (HCl)m complexes in and on large Arn clusters

    NASA Astrophysics Data System (ADS)

    Nahler, N. Hendrik; Fárník, Michal; Buck, Udo; Vach, Holger; Gerber, R. Benny

    2004-07-01

    Photodissociation experiments were carried out at 193 nm for single HCl molecules which are adsorbed on the surface of large Arn clusters and small (HCl)m complexes which are embedded in the interior of these clusters. For the surface case the size dependence is measured for the average sizes =140-1000. No cage exit events are observed in agreement with the substitutional position of the molecule deeply buried in the outermost shell. This result is confirmed by a molecular dynamics simulation of the pickup process under realistic conditions concerning the experiment and the interaction potentials. The calculations of the dissociation process employ the surface hopping model. For the embedded case the average sizes covered are =3 and 6 and =8-248. The kinetic energy of the H atom fragments is measured exhibiting peaks at zero and around 2.0 eV which mark completely caged and unperturbed fragments, respectively. The ratio of theses peaks strongly depends on the cluster size and agrees well with theoretical predictions for one and two closed icosahedral shells, in which the nonadiabatic coupling of all states was accounted for.

  19. Hydrogen activation by unsaturated mixed-metal cluster complexes: new directions.

    PubMed

    Adams, Richard D; Captain, Burjor

    2008-01-01

    There has been a renewed interest in the chemistry of hydrogen as a result of the ever-increasing global demands for energy. Recent studies have revealed new electronically unsaturated polynuclear metal complexes containing bulky ligands that exhibit a variety of reactions with hydrogen, including facile addition and elimination under mild conditions. Materials and molecules that can reversibly absorb large quantities of hydrogen are very attractive for hydrogen storage and hydrogenation catalysis. This Minireview summarizes recent studies of reactions of hydrogen with unsaturated mixed-metal cluster complexes containing platinum and bulky phosphine ligands. Some related studies on bimetallic cooperativity and the synthesis of trimetallic nanoparticles on mesoporous supports that exhibit high activity and selectivity for catalytic hydrogenations are also discussed.

  20. Tunable diode laser spectrometer for pulsed supersonic jets: application to weakly-bound complexes and clusters.

    PubMed

    Brookes, Matthew D; Xia, Changhong; Tang, Jian; Anstey, James A; Fulsom, Bryan G; Au Yong, Ke-Xian; King, Jenna M; McKellar, A R W

    2004-12-01

    The design and operation of an apparatus for studying infrared spectra of weakly-bound complexes is described in detail. A pulsed supersonic jet expansion is probed using a tunable Pb-salt diode laser spectrometer operated in a rapid-scan mode. The jet may be fitted with either pinhole or slit shaped nozzles, the former giving lower effective rotational temperatures, and the latter giving sharper spectral lines. Notable features of the apparatus include use of a toroidal multi-pass mirror system to give over 100 passes of the laser through the supersonic jet, use of the normal laser controller for laser sweeping during both setup and data acquisition, and use of a simple semi-automated wavenumber calibration procedure. Performance of the apparatus is illustrated with observed spectra of the van der Waals complex He-OCS, and the seeded helium clusters He(N)-OCS and He(N)-CO.

  1. Communication: Analytic gradients for the complex absorbing potential equation-of-motion coupled-cluster method

    NASA Astrophysics Data System (ADS)

    Benda, Zsuzsanna; Jagau, Thomas-C.

    2017-01-01

    The general theory of analytic energy gradients is presented for the complex absorbing potential equation-of-motion coupled-cluster (CAP-EOM-CC) method together with an implementation within the singles and doubles approximation. Expressions for the CAP-EOM-CC energy gradient are derived based on a Lagrangian formalism with a special focus on the extra terms arising from the presence of the CAP. Our implementation allows for locating minima on high-dimensional complex-valued potential energy surfaces and thus enables geometry optimizations of resonance states of polyatomic molecules. The applicability of our CAP-EOM-CC gradients is illustrated by computations of the equilibrium structures and adiabatic electron affinities of the temporary anions of formaldehyde, formic acid, and ethylene. The results are compared to those obtained from standard EOM-CC calculations and the advantages of CAP methods are emphasized.

  2. CHEMICAL ABUNDANCES IN NGC 5053: A VERY METAL-POOR AND DYNAMICALLY COMPLEX GLOBULAR CLUSTER

    SciTech Connect

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico

    2015-05-10

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin–Indiana–Yale–NOAO–Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ∼ 75–90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of −2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na–O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  3. Chemical Abundances in NGC 5053: A Very Metal-poor and Dynamically Complex Globular Cluster

    NASA Astrophysics Data System (ADS)

    Boberg, Owen M.; Friel, Eileen D.; Vesperini, Enrico

    2015-05-01

    NGC 5053 provides a rich environment to test our understanding of the complex evolution of globular clusters (GCs). Recent studies have found that this cluster has interesting morphological features beyond the typical spherical distribution of GCs, suggesting that external tidal effects have played an important role in its evolution and current properties. Additionally, simulations have shown that NGC 5053 could be a likely candidate to belong to the Sagittarius dwarf galaxy (Sgr dSph) stream. Using the Wisconsin-Indiana-Yale-NOAO-Hydra multi-object spectrograph, we have collected high quality (signal-to-noise ratio ˜ 75-90), medium-resolution spectra for red giant branch stars in NGC 5053. Using these spectra we have measured the Fe, Ca, Ti, Ni, Ba, Na, and O abundances in the cluster. We measure an average cluster [Fe/H] abundance of -2.45 with a standard deviation of 0.04 dex, making NGC 5053 one of the most metal-poor GCs in the Milky Way (MW). The [Ca/Fe], [Ti/Fe], and [Ba/Fe] we measure are consistent with the abundances of MW halo stars at a similar metallicity, with alpha-enhanced ratios and slightly depleted [Ba/Fe]. The Na and O abundances show the Na-O anti-correlation found in most GCs. From our abundance analysis it appears that NGC 5053 is at least chemically similar to other GCs found in the MW. This does not, however, rule out NGC 5053 being associated with the Sgr dSph stream.

  4. Lipid Clustering Correlates with Membrane Curvature as Revealed by Molecular Simulations of Complex Lipid Bilayers

    PubMed Central

    Koldsø, Heidi; Shorthouse, David; Hélie, Jean; Sansom, Mark S. P.

    2014-01-01

    Cell membranes are complex multicomponent systems, which are highly heterogeneous in the lipid distribution and composition. To date, most molecular simulations have focussed on relatively simple lipid compositions, helping to inform our understanding of in vitro experimental studies. Here we describe on simulations of complex asymmetric plasma membrane model, which contains seven different lipids species including the glycolipid GM3 in the outer leaflet and the anionic lipid, phosphatidylinositol 4,5-bisphophate (PIP2), in the inner leaflet. Plasma membrane models consisting of 1500 lipids and resembling the in vivo composition were constructed and simulations were run for 5 µs. In these simulations the most striking feature was the formation of nano-clusters of GM3 within the outer leaflet. In simulations of protein interactions within a plasma membrane model, GM3, PIP2, and cholesterol all formed favorable interactions with the model α-helical protein. A larger scale simulation of a model plasma membrane containing 6000 lipid molecules revealed correlations between curvature of the bilayer surface and clustering of lipid molecules. In particular, the concave (when viewed from the extracellular side) regions of the bilayer surface were locally enriched in GM3. In summary, these simulations explore the nanoscale dynamics of model bilayers which mimic the in vivo lipid composition of mammalian plasma membranes, revealing emergent nanoscale membrane organization which may be coupled both to fluctuations in local membrane geometry and to interactions with proteins. PMID:25340788

  5. Lipid clustering correlates with membrane curvature as revealed by molecular simulations of complex lipid bilayers.

    PubMed

    Koldsø, Heidi; Shorthouse, David; Hélie, Jean; Sansom, Mark S P

    2014-10-01

    Cell membranes are complex multicomponent systems, which are highly heterogeneous in the lipid distribution and composition. To date, most molecular simulations have focussed on relatively simple lipid compositions, helping to inform our understanding of in vitro experimental studies. Here we describe on simulations of complex asymmetric plasma membrane model, which contains seven different lipids species including the glycolipid GM3 in the outer leaflet and the anionic lipid, phosphatidylinositol 4,5-bisphophate (PIP2), in the inner leaflet. Plasma membrane models consisting of 1500 lipids and resembling the in vivo composition were constructed and simulations were run for 5 µs. In these simulations the most striking feature was the formation of nano-clusters of GM3 within the outer leaflet. In simulations of protein interactions within a plasma membrane model, GM3, PIP2, and cholesterol all formed favorable interactions with the model α-helical protein. A larger scale simulation of a model plasma membrane containing 6000 lipid molecules revealed correlations between curvature of the bilayer surface and clustering of lipid molecules. In particular, the concave (when viewed from the extracellular side) regions of the bilayer surface were locally enriched in GM3. In summary, these simulations explore the nanoscale dynamics of model bilayers which mimic the in vivo lipid composition of mammalian plasma membranes, revealing emergent nanoscale membrane organization which may be coupled both to fluctuations in local membrane geometry and to interactions with proteins.

  6. STAR CLUSTER COMPLEXES AND THE HOST GALAXY IN THREE H II GALAXIES: Mrk 36, UM 408, AND UM 461

    SciTech Connect

    Lagos, P.; Telles, E.; Nigoche-Netro, A.

    2011-11-15

    We present a stellar population study of three H II galaxies (Mrk 36, UM 408, and UM 461) based on the analysis of new ground-based high-resolution near-infrared J, H, and K{sub p} broadband and Br{gamma} narrowband images obtained with Gemini/NIRI. We identify and determine the relative ages and masses of the elementary star clusters and/or star cluster complexes of the starburst regions in each of these galaxies by comparing the colors with evolutionary synthesis models that include the contribution of stellar continuum, nebular continuum, and emission lines. We found that the current star cluster formation efficiency in our sample of low-luminosity H II galaxies is {approx}10%. Therefore, most of the recent star formation is not in massive clusters. Our findings seem to indicate that the star formation mode in our sample of galaxies is clumpy, and that these complexes are formed by a few massive star clusters with masses {approx}>10{sup 4} M{sub Sun }. The age distribution of these star cluster complexes shows that the current burst started recently and likely simultaneously over short timescales in their host galaxies, triggered by some internal mechanism. Finally, the fraction of the total cluster mass with respect to the low surface brightness (or host galaxy) mass, considering our complete range in ages, is less than 1%.

  7. Spatiotemporal Clustering of Mycobacterium tuberculosis Complex Genotypes in Florida: Genetic Diversity Segregated by Country of Birth

    PubMed Central

    Séraphin, Marie Nancy; Lauzardo, Michael; Morris, J. Glenn; Blackburn, Jason K.

    2016-01-01

    Background Tuberculosis (TB) is caused by members of the Mycobacterium tuberculosis complex (MTBC). Although the MTBC is highly clonal, between-strain genetic diversity has been observed. In low TB incidence settings, immigration may facilitate the importation of MTBC strains with a potential to complicate TB control efforts. Methods We investigated the genetic diversity and spatiotemporal clustering of 2,510 MTBC strains isolated in Florida, United States, between 2009 and 2013 and genotyped using spoligotyping and 24-locus MIRU-VNTR. We mapped the genetic diversity to the centroid of patient residential zip codes using a geographic information system (GIS). We assessed transmission dynamics and the influence of immigration on genotype clustering using space-time permutation models adjusted for foreign-born population density and county-level HIV risk and multinomial models stratified by country of birth and timing of immigration in SaTScan. Principal Findings Among the 2,510 strains, 1,245 were reported among foreign-born persons; including 408 recent immigrants (<5 years). Strain allelic diversity (h) ranged from low to medium in most locations and was most diverse in urban centers where foreign-born population density was also high. Overall, 21.5% of cases among U.S.-born persons and 4.6% among foreign-born persons clustered genotypically and spatiotemporally and involved strains of the Haarlem family. One Haarlem space-time cluster identified in the mostly rural northern region of Florida included US/Canada-born individuals incarcerated at the time of diagnosis; two clusters in the mostly urban southern region of Florida were composed predominantly of foreign-born persons. Both groups had HIV prevalence above twenty percent. Conclusions/Significance Almost five percent of TB cases reported in Florida during 2009–2013 were potentially due to recent transmission. Improvements to TB screening practices among the prison population and recent immigrants are

  8. The merger history of the complex cluster Abell 1758: a combined weak lensing and spectroscopic view

    NASA Astrophysics Data System (ADS)

    Monteiro-Oliveira, R.; Cypriano, E. S.; Machado, R. E. G.; Lima Neto, G. B.; Ribeiro, A. L. B.; Sodré, L.; Dupke, R.

    2017-04-01

    We present a weak-lensing and dynamical study of the complex cluster Abell 1758 (A1758, bar{z} = 0.278) supported by hydrodynamical simulations. This cluster is composed of two main structures called A1758N and A1758S. The northern structure is composed of A1758NW and A1758NE, with lensing determined masses of 7.90_{-1.55}^{+1.89} × 1014 M⊙ and 5.49_{-1.33}^{+1.67} × 1014 M⊙, respectively. They show a remarkable feature: while in A1758NW, there is a spatial agreement among weak-lensing mass distribution, intracluster medium and its brightest cluster galaxy (BCG), in A1758NE, the X-ray peak is located 96_{-15}^{+14} arcsec away from the mass peak and BCG positions. Given the detachment between gas and mass, we could use the local surface mass density to estimate an upper limit for the dark matter self-interaction cross-section: σ/m < 5.83 cm2 g-1. Combining our velocity data with hydrodynamical simulations, we have shown that A1758 NW and NE had their closest approach 0.27 Gyr ago and their merger axis is 21° ± 12° from the plane of the sky. In the A1758S system, we have measured a total mass of 4.96_{-1.19}^{+1.08} × 10^{14} M⊙ and, using radial velocity data, we found that the main merger axis is located at 70° ± 4° from the plane of the sky, therefore closest to the line of sight.

  9. New Constraints on a Complex Relation between Globular Cluster Colors and Environment

    NASA Astrophysics Data System (ADS)

    Powalka, Mathieu; Puzia, Thomas H.; Lançon, Ariane; Peng, Eric W.; Schönebeck, Frederik; Alamo-Martínez, Karla; Ángel, Simón; Blakeslee, John P.; Côté, Patrick; Cuillandre, Jean-Charles; Duc, Pierre-Alain; Durrell, Patrick; Ferrarese, Laura; Grebel, Eva K.; Guhathakurta, Puragra; Gwyn, S. D. J.; Kuntschner, Harald; Lim, Sungsoon; Liu, Chengze; Lyubenova, Mariya; Mihos, J. Christopher; Muñoz, Roberto P.; Ordenes-Briceño, Yasna; Roediger, Joel; Sánchez-Janssen, Rubén; Spengler, Chelsea; Toloba, Elisa; Zhang, Hongxin

    2016-09-01

    We present an analysis of high-quality photometry for globular clusters (GCs) in the Virgo cluster core region, based on data from the Next Generation Virgo Cluster Survey (NGVS) pilot field, and in the Milky Way (MW), based on Very Large Telescope/X-Shooter spectrophotometry. We find significant discrepancies in color-color diagrams between sub-samples from different environments, confirming that the environment has a strong influence on the integrated colors of GCs. GC color distributions along a single color are not sufficient to capture the differences we observe in color-color space. While the average photometric colors become bluer with increasing radial distance to the cD galaxy M87, we also find a relation between the environment and the slope and intercept of the color-color relations. A denser environment seems to produce a larger dynamic range in certain color indices. We argue that these results are not due solely to differential extinction, Initial Mass Function variations, calibration uncertainties, or overall age/metallicity variations. We therefore suggest that the relation between the environment and GC colors is, at least in part, due to chemical abundance variations, which affect stellar spectra and stellar evolution tracks. Our results demonstrate that stellar population diagnostics derived from model predictions which are calibrated on one particular sample of GCs may not be appropriate for all extragalactic GCs. These results advocate a more complex model of the assembly history of GC systems in massive galaxies that goes beyond the simple bimodality found in previous decades.

  10. Predicting Water Activity for Complex Wastes with Solvation Cluster Equilibria (SCE) - 12042

    SciTech Connect

    Agnew, S.F.; Reynolds, J.G.; Johnston, C.T.

    2012-07-01

    Predicting an electrolyte mixture's water activity, i.e. the ratio of water vapor pressure over a solution with that of pure water, in principle reveals both boiling point and solubilities for that mixture. Better predictions of these properties helps support the ongoing missions to concentrate complex nuclear waste mixtures in order to conserve tank space and improved predictions of water activity will help. A new approach for predicting water activity, the solvation cluster equilibria (SCE) model, uses pure electrolyte water activities to predict water activity for a complex mixture of those electrolytes. An SCE function based on electrolyte hydration free energy and a standard Debye- Hueckel (DH) charge compression fits each pure electrolyte's water activity with three parameters. Given these pure electrolyte water activities, the SCE predicts any mixture water activity over a large range of concentration with an additional parameter for each mixture vector, the multinarity. In contrast to ionic strength, which scales with concentration, multinarity is related to the relative proportion of electrolytes in a mixture and can either increase or decrease the water activity prediction over a broad range of concentration for that mixture. The SCE model predicts water activity for complex electrolyte mixtures based on the water activities of pure electrolytes. Three parameter SCE functions fit the water activities of pure electrolytes and along with a single multinarity parameter for each mixture vector then predict the mixture water activity. Predictions of water activity can in principle predict solution electrolyte activity and this relationship will be explored in the future. Predicting electrolyte activities for complex mixtures provides a means of determining solubilities for each electrolyte. Although there are a number of reports [9, 10, 11] of water activity models for pure and binary mixtures of electrolytes, none of them compare measured versus calculated

  11. Cluster perturbation theory for the self-assembly of associating fluids into complex structures.

    PubMed

    Marshall, Bennett D

    2014-12-01

    Wertheim's two-density thermodynamic perturbation theory (TPT) has proven to be an indispensable statistical mechanical tool in the description of associating fluids with a single association site. TPT was developed to enforce the monovalence of the hydrogen bond and only recently has been extended to account for divalent association sites. It has been shown through experiment and molecular simulation that certain one-site associating fluids can self-assemble into complex extended supramolecular structures as a result of multiple bonding of association sites. In this paper we reorganize TPT into a form that is more easily applied to complex associated structures. The derived theory is general to all possible self-assemble structures. We obtain the free energy and bonding fractions in a general way in terms of single-cluster partition functions and averages. The new formalism removes any reference to graph theory allowing for the conceptually straightforward application of the two-density formalism to complex self-assembled structures.

  12. Investigating tunnel and above-barrier ionization using complex-scaled coupled-cluster theory

    NASA Astrophysics Data System (ADS)

    Jagau, Thomas-C.

    2016-11-01

    The theory and implementation of the complex-scaled coupled-cluster method with singles and doubles excitations (cs-CCSD) for studying resonances induced by static electric fields are presented. Within this framework, Stark shifts and ionization rates are obtained directly from the real and imaginary parts of the complex energy. The method is applied to the ground states of hydrogen, helium, lithium, beryllium, neon, argon, and carbon at varying field strengths. Complex-scaled Hartree-Fock, second-order many-body perturbation theory, and CCSD results are reported and analyzed with a focus on the impact of electron correlation on the ionization process. cs-CCSD calculations with suitably augmented standard Gaussian basis sets are found to deliver accurate strong-field ionization rates over a range of six orders of magnitude. The field-induced resonances are characterized beyond energy and ionization rate through their dipole moments, second moments, as well as Dyson orbitals and comparisons are drawn to autoionizing and autodetaching resonances. Marked differences are found between the tunneling and above-barrier regimes allowing for a clear distinction of the two mechanisms.

  13. The contribution of cluster and discriminant analysis to the classification of complex aquifer systems.

    PubMed

    Panagopoulos, G P; Angelopoulou, D; Tzirtzilakis, E E; Giannoulopoulos, P

    2016-10-01

    This paper presents an innovated method for the discrimination of groundwater samples in common groups representing the hydrogeological units from where they have been pumped. This method proved very efficient even in areas with complex hydrogeological regimes. The proposed method requires chemical analyses of water samples only for major ions, meaning that it is applicable to most of cases worldwide. Another benefit of the method is that it gives a further insight of the aquifer hydrogeochemistry as it provides the ions that are responsible for the discrimination of the group. The procedure begins with cluster analysis of the dataset in order to classify the samples in the corresponding hydrogeological unit. The feasibility of the method is proven from the fact that the samples of volcanic origin were separated into two different clusters, namely the lava units and the pyroclastic-ignimbritic aquifer. The second step is the discriminant analysis of the data which provides the functions that distinguish the groups from each other and the most significant variables that define the hydrochemical composition of the aquifer. The whole procedure was highly successful as the 94.7 % of the samples were classified to the correct aquifer system. Finally, the resulted functions can be safely used to categorize samples of either unknown or doubtful origin improving thus the quality and the size of existing hydrochemical databases.

  14. Hyperspectral clustering and unmixing for studying the ecology of state formation and complex societies

    NASA Astrophysics Data System (ADS)

    Kwong, Justin D.; Messinger, David W.; Middleton, William D.

    2009-08-01

    This project is an application of hyperspectral classification and unmixing in support of an ongoing archaeological study. The study region is the Oaxaca Valley located in the state of Oaxaca, Mexico on the southern coast. This was the birthplace of the Zapotec civilization which grew into a complex state level society. Hyperion imagery is being collected over a 30,000 km2 area. Classification maps of regions of interest are generated using K-means clustering and a novel algorithm called Gradient Flow. Gradient Flow departs from conventional stochastic or deterministic approaches, using graph theory to cluster spectral data. Spectral unmixing is conducted using the RIT developed algorithm Max-D to automatically find end members. Stepwise unmixing is performed to better model the data using the end members found be Max-D. Data are efficiently shared between imaging scientists and archaeologists using Google Earth to stream images over the internet rather than downloading them. The overall goal of the project is to provide archaeologists with useful information maps without having to interpret the raw data.

  15. Complexes of DNA bases and Watson-Crick base pairs with small neutral gold clusters.

    PubMed

    Kryachko, E S; Remacle, F

    2005-12-08

    The nature of the DNA-gold interaction determines and differentiates the affinity of the nucleobases (adenine, thymine, guanine, and cytosine) to gold. Our preliminary computational study [Kryachko, E. S.; Remacle, F. Nano Lett. 2005, 5, 735] demonstrates that two major bonding factors govern this interaction: the anchoring, either of the Au-N or Au-O type, and the nonconventional N-H...Au hydrogen bonding. In this paper, we offer insight into the nature of nucleobase-gold interactions and provide a detailed characterization of their different facets, i.e., geometrical, energetic, and spectroscopic aspects; the gold cluster size and gold coordination effects; proton affinity; and deprotonation energy. We then investigate how the Watson-Crick DNA pairing patterns are modulated by the nucleobase-gold interaction. We do so in terms of the proton affinities and deprotonation energies of those proton acceptors and proton donors which are involved in the interbase hydrogen bondings. A variety of properties of the most stable Watson-Crick [A x T]-Au3 and [G x C]-Au3 hybridized complexes are described and compared with the isolated Watson-Crick A x T and G x C ones. It is shown that enlarging the gold cluster size to Au6 results in a rather short gold-gold bond in the Watson-Crick interbase region of the [G x C]-Au6 complex that bridges the G x C pair and thus leads to a significant strengthening of G x C pairing.

  16. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    SciTech Connect

    Liang, Wenchuan

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  17. Synthesis and structural characterization of ruthenium carbonyl cluster complexes containing platinum with a bulky N-heterocyclic carbene ligand.

    PubMed

    Saha, Sumit; Captain, Burjor

    2014-01-21

    The reaction of Ru3(CO)12 with Pt(IMes)2 in benzene solvent at room temperature afforded the monoplatinum-triruthenium cluster complex Ru3Pt(IMes)2(CO)11, 1, in 21% yield and the trigonal bipyramidal cluster complex Ru3Pt2(IMes)2(CO)12, 2, in 26% yield. The reaction of Ru(CO)5 with Pt(IMes)2 in benzene solvent at 0 °C yielded two trinuclear cluster complexes, the monoplatinum-diruthenium Ru2Pt(IMes)(CO)9, 3, and the monoruthenium-diplatinum cluster complex RuPt2(IMes)2(CO)6, 4. The reaction of 2 with hydrogen at 80 °C afforded the tetrahydrido-tetraruthenium complex Ru4(IMes)(CO)11(μ-H)4, 5, and the dihydrido-diruthenium-diplatinum complex Ru2Pt2(IMes)2(CO)8(μ-H)2, 6. All six compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  18. CHIMERA: Top-down model for hierarchical, overlapping and directed cluster structures in directed and weighted complex networks

    NASA Astrophysics Data System (ADS)

    Franke, R.

    2016-11-01

    In many networks discovered in biology, medicine, neuroscience and other disciplines special properties like a certain degree distribution and hierarchical cluster structure (also called communities) can be observed as general organizing principles. Detecting the cluster structure of an unknown network promises to identify functional subdivisions, hierarchy and interactions on a mesoscale. It is not trivial choosing an appropriate detection algorithm because there are multiple network, cluster and algorithmic properties to be considered. Edges can be weighted and/or directed, clusters overlap or build a hierarchy in several ways. Algorithms differ not only in runtime, memory requirements but also in allowed network and cluster properties. They are based on a specific definition of what a cluster is, too. On the one hand, a comprehensive network creation model is needed to build a large variety of benchmark networks with different reasonable structures to compare algorithms. On the other hand, if a cluster structure is already known, it is desirable to separate effects of this structure from other network properties. This can be done with null model networks that mimic an observed cluster structure to improve statistics on other network features. A third important application is the general study of properties in networks with different cluster structures, possibly evolving over time. Currently there are good benchmark and creation models available. But what is left is a precise sandbox model to build hierarchical, overlapping and directed clusters for undirected or directed, binary or weighted complex random networks on basis of a sophisticated blueprint. This gap shall be closed by the model CHIMERA (Cluster Hierarchy Interconnection Model for Evaluation, Research and Analysis) which will be introduced and described here for the first time.

  19. Oxovanadium(V) 1,3-propanediolate chloride complexes: Tetrameric clusters

    SciTech Connect

    Crans, D.C.; Marshman, R.W.; Gottlieb, M.S.; Anderson, O.P.; Miller, M.M. )

    1992-11-25

    Structural, spectroscopic, and catalytic studies of oxovanadium-(V) alkoxide chlorides have shown that these compounds are monomeric and exhibit activities as oxidation catalysts and Lewis acids. The structure of the reaction product of VOCl[sub 3] and various 1,3-propanediol derivatives was characterized in solution at various temperatures using multinuclear NMR spectroscopy. Although oxovanadium dialkoxide chlorides tend to be monomeric, 1,3-propanediol derivatives induce cluster formation generating tetrameric complexes with a molecular formula of (VOC1L)[sub 4] (where L is bidentate). The 1,3-propanediol derivatives preferred to bridge over two (or three) vanadium atoms rather than form a cyclic six-membered ring on one vanadium atom as found with the corresponding phosphorus compounds. When the 1,3-propanediol ligand was asymmetric, several complexes were observed in solution. A hydrolysis product was characterized by X-ray crystallography. The compound crystallizes in the triclinic space group P[bar 1] with a = 10.003 (2) [Angstrom], b = 11.462 (3) [Angstrom], c = 11.699 (2) [Angstrom], [alpha] = 65.72 (2)[degrees], [beta] = 79.81 (2)[degrees], [gamma] = 81.89 (2) [degrees], V = 1199.7 (4) [Angstrom][sup 3], and Z = 1. The correlation between solution and solid-state structure was determined, and a possible pathway to the hydrolysis product was suggested. Vanadium is used as a reagent in organic synthesis; however, these studies suggest that altered reactivities may surface in the presence of 1,3-propanediol ligands or substrates. The studies show that the analogy between phosphorus and vanadium breaks down in complexes containing 1,3-propanediol derivatives, reducing the prospects of chemically preparing vanadium analogs of cAMP.

  20. Thiophenol and thiophenol radical and their complexes with gold clusters Au 5 and Au 6

    NASA Astrophysics Data System (ADS)

    Remacle, F.; Kryachko, E. S.

    2004-12-01

    The longstanding controversy between experiment and theory regarding which conformer of thiophenol, planar or perpendicular, is the most stable and what is the magnitude of the corresponding rotational barrier of the S-H group is discussed. We propose a variety of rather modest high-level computational methods within the density theory, which corroborate the experimental data. These methods demonstrate that the planar structure of thiophenol is the most stable and the magnitude of the rotational barrier falls within the experimental range of 3.35±0.84 kJ mol -1. However, the barrier is of the order of RT at room temperature, which might prevent to clearly identify the most stable conformer of thiophenol in experiments and leads to a large-amplitude motion of the thiolic hydrogen. On the other hand, such low value of the barrier may lead to some error in evaluating the thermodynamic properties of thiophenol within the rigid-rotor-harmonic oscillator model, in particular for the bond dissociation enthalpy. We also show the existence of a large entropy contribution to the Gibbs free energy difference between the planar and perpendicular conformers which is the order of the rotational barrier (≈4 kJ mol -1). This might be of interest for experimental study. The most stable complexes of thiophenol with the gold clusters Au 5 and Au 6 are also investigated. It is shown that the sulfur atom prefers to anchor to two- and three-coordinated atoms of gold in these clusters to form a strongly directional gold-sulfur bond. The hydrogen abstraction from the S-H group of thiophenol bonded to the two-coordinated gold atom in Au 5 yields the bridging Au-S dibond and results in a spectacular reduction of the bond dissociation energy of thiophenol by nearly a factor of three.

  1. VizieR Online Data Catalog: Galaxies in the UMa cluster complex (Karachentsev+, 2013)

    NASA Astrophysics Data System (ADS)

    Karachentsev, I. D.; Nasonova, O. G.; Courtois, H. M.

    2015-04-01

    A nearby friable cloud in Ursa Majoris contains 270 galaxies with radial velocities 500complex. According to Makarov & Karachentsev (2011MNRAS.412.2498M, Cat. J/MNRAS/412/2498), most of the UMa galaxies belong to seven bound groups, which have the following median parameters: velocity dispersion of 58k/s, harmonic projected radius of 300kpc, virial mass of 2x1012M⊙ and virial mass-to-K-band luminosity ratio of 27M⊙/L⊙. Almost a half of the UMa cloud population are gas-rich dwarfs (Ir, Im, BCD) with active star formation seen in the GALEX UV-survey. The UMa groups reside within 15-19Mpc from us, being just at the same distance as the Virgo cluster. The total virial mass of the UMa groups is 4x1013M⊙, yielding the average density of dark matter in the UMa cloud to be Ωm=0.08, i.e. a factor of 3 lower than the cosmic average. This is despite the fact that the UMa cloud resides in a region of the Universe that is an apparent overdensity. A possible explanation for this is that most mass in the Universe lies in the empty space between clusters. Herewith, the mean distances and velocities of the UMa groups follow nearly undisturbed Hubble flow without a sign of the 'Z-wave' effect caused by infall towards a massive attractor. This constrains the total amount of dark matter between the UMa groups within the cloud volume. (1 data file).

  2. A Chemical Composition Survey of the Iron-complex Globular Cluster NGC 6273 (M19)

    NASA Astrophysics Data System (ADS)

    Johnson, Christian I.; Caldwell, Nelson; Rich, R. Michael; Mateo, Mario; Bailey, John I., III; Clarkson, William I.; Olszewski, Edward W.; Walker, Matthew G.

    2017-02-01

    Recent observations have shown that a growing number of the most massive Galactic globular clusters contain multiple populations of stars with different [Fe/H] and neutron-capture element abundances. NGC 6273 has only recently been recognized as a member of this “iron-complex” cluster class, and we provide here a chemical and kinematic analysis of >300 red giant branch and asymptotic giant branch member stars using high-resolution spectra obtained with the Magellan–M2FS and VLT–FLAMES instruments. Multiple lines of evidence indicate that NGC 6273 possesses an intrinsic metallicity spread that ranges from about [Fe/H] = ‑2 to ‑1 dex, and may include at least three populations with different [Fe/H] values. The three populations identified here contain separate first (Na/Al-poor) and second (Na/Al-rich) generation stars, but a Mg–Al anti-correlation may only be present in stars with [Fe/H] ≳ ‑1.65. The strong correlation between [La/Eu] and [Fe/H] suggests that the s-process must have dominated the heavy element enrichment at higher metallicities. A small group of stars with low [α/Fe] is identified and may have been accreted from a former surrounding field star population. The cluster’s large abundance variations are coupled with a complex, extended, and multimodal blue horizontal branch (HB). The HB morphology and chemical abundances suggest that NGC 6273 may have an origin that is similar to ω Cen and M54. Based on observations made 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. These observations are associated with program GO-14197. This paper includes data gathered with the 6.5 m Magellan Telescopes located as Las Campanas Observatory, Chile.

  3. Nucleophilic ring opening of bridging thietane ligands in trirhenium carbonyl cluster complexes

    SciTech Connect

    Adams, R.D.; Cortopassi, J.E.; Falloon, S.B.

    1992-11-01

    The reactions of 3,3-dimethylthietane, SCH{sub 2}CMe{sub 2}CH{sub 2} (3,3-DMT), and thietane, SCH{sub 2}CH{sub 2}CH{sub 2}, with Re{sub 3}(CO){sub 10}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}]({mu}-H){sub 3}, 2b. Compound 2a was characterized crystallographically and was found to consist of a trirhenium cluster with three bridging hydride ligands and a bridging thietane ligand coordinated through its sulfur atom. 2a and 2b react with halide ions by ring-opening additions to the 3,3-DMT ligand to yield the complex anions [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}x)({mu}-h){sub 3}]{sup -} 3A-6A, X = F (71%), Cl(71%), Br(84%), I(87%) and [Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl)({mu}-H){sub 3}]{sup -}, 4b (67%). Similarly, addition of NMe{sub 3} to 2a and 2b yielded the ring-opened zwitterions Re{sub 3}(CO){sub 10}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}NMe{sub 3})({mu}-H){sub 3}, 7 a crystographically. They are zwitterions positively charged at the nitrogen atoms and negatively charged on the trirhenium clusters. Complex 7b was also obtained in a 48% yield from the reaction of Re{sub 3}(C){sub 12}({mu}-H){sub 3} with Me{sub 3}NO in the presence of thietane, but the corresponding reaction using 3,3-DMT yielded only 2a and Re{sub 3}(CO){sub 11}(SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}-H){sub 3}, 8. Attempts to obtain a ring-opening addition to 2a by reaction with PMe{sub 2}Ph yielded only Re{sub 3}(CO){sub 10}(PMe{sub 2}PH){sub 2}({mu}-H){sub 3} by ligand substitution. Attempts to obtain ring opening addition to 8 by reaction with I{sup -} yielded only [Re{sub 3}(CO){sub 11}I({mu}-H){sub 3}]{sup -} by ligand substitution. 20 refs., 3 figs., 10 tabs.

  4. Nucleophilic ring opening of bridging thietanes in open triosmium cluster complexes

    SciTech Connect

    Adams, R.D.; Belinski, J.A.

    1992-07-01

    The complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}] (1) and Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}] (2) were obtained from the reactions of Os{sub 3}(CO){sub 10}({mu}{sub 3}-S) with 3,3-dimethylthietane (DMT) and thietane, respectively, at -42 {degree}C in the presence of Me{sub 3}NO. Compound 1 was characterized by a single-crystal X-ray diffraction analysis and was found to contain a DMT group bridging two of the nonbonded metal atoms in the open cluster of three metal atoms by using both lone pairs of electrons on the sulfur atom. Compound 1 reacted with bis(triphenylphosphine)nitrogen(1+) chloride ([PPN]Cl) at 25 {degrees}C to yield the salt [PPN][Os{sub 3}-(CO){sub 9}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}{sub 3}-S)] (3; 76%), in which the chloride ion was added to one of the methylene groups of the DMT ring in a process that caused the ring to open by cleavage of one of the carbon-sulfur bonds. A 4-chloro-3,3-dimethylpropanethiolate ligand bridges the open edge of the anionic triosmium cluster. Compound 3 was converted to the neutral complex Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (4) by reaction with HCl at 25 {degrees}C. Compound 4 is structurally similar to 3, except that is contains a hydride ligand bridging one of the two metal-metal bonds. Compounds 1 and 2 react with HCl in CH{sub 2}Cl{sub 2} solvent to yield the neutral compounds 4 and Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (5) in 89% and 90% yields, respectively, in one step. 11 refs., 3 figs., 10 tabs.

  5. Zeolite-supported rhodium complexes and clusters: switching catalytic selectivity by controlling structures of essentially molecular species.

    PubMed

    Serna, Pedro; Gates, B C

    2011-04-06

    Precise synthesis and characterization of site-isolated rhodium complexes and extremely small rhodium clusters supported on zeolite HY allow control of the catalyst selectivity in the conversion of ethene to n-butene or ethane, respectively, as a result of tuning the structure of the active sites at a molecular level.

  6. Carbonyl substitution chemistry of some trimetallic transition metal cluster complexes with polyfunctional ligands

    SciTech Connect

    Byrne, Lindsay T.; Hondow, Nicole S.; Koutsantonis, George A.; Skelton, Brian W.; Torabi, A. Asgar; White, Allan H.; Wild, S. Bruce

    2008-11-03

    The trimetallic clusters [Ru{sub 3}(CO){sub 10}(dppm)], [Ru{sub 3}(CO){sub 12}] and [RuCo{sub 2}(CO){sub 11}] react with a number of multifunctional secondary phosphine and tertiary arsine ligands to give products consequent on carbonyl substitution and, in the case of the secondary phosphines, PH activation. The reaction with the unresolved mixed P/S donor, 1-phenylphosphino-2-thio(ethane), HSCH{sub 2}CH{sub 2}PHPh ({double_bond}LH{sub 2}), gave two products under various conditions which have been characterized by spectroscopic and crystallographic means. These two complexes [Ru{sub 3}({mu}dppm)(H)(CO){sub 7}(LH)] and [Ru{sub 3}({mu}-dppm)(H)(CO){sub 8}(LH)Ru{sub 3}({mu}-dppm)(CO){sub 9}], show the versatility of the ligand, with it chelating in the former and bridging two Ru{sub 3} units in the latter. The stereogenic centres in the molecules gave rise to complicated spectroscopic data which are consistent with the presence of diastereoisomers. In the case of [Ru{sub 3}(CO){sub 12}] the reaction with LH{sub 2} gave a poor yield of a tetranuclear butterfly cluster, [Ru{sub 4}(CO){sub 10}(L){sub 2}], in which two of the ligands bridge opposite hinge wingtip bonds of the cluster. A related ligand, HSCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe), reacted with [RuCo{sub 2}(CO){sub 11}] to give a low yield of the heterobimetallic Ru-Co adduct, [RuCo(CO){sub 6}(SCH{sub 2}CH{sub 2}AsMe(C{sub 6}H{sub 4}CH{sub 2}OMe))], which appears to be the only one of its type so far structurally characterized. The secondary phosphine, HPMe(C{sub 6}H{sub 4}(CH{sub 2}OMe)) and its oxide HP(O)Me(C{sub 6}H{sub 4}(CH{sub 2}OMe)) also react with the cluster [Ru{sub 3}(CO){sub 10}(dppm)] to give carbonyl substitution products, [Ru{sub 3}(CO){sub 5}(dppm)({mu}{sub 2}-PMe(C{sub 6}H{sub 4}CH{sub 2}OMe)){sub 4}], and [Ru{sub 3}H(CO){sub 7}(dppm)({mu}{sub 2},{eta}{sup 1}P({double_bond}O)Me(C{sub 6}H{sub 4}CH{sub 2}OMe))]. The former consists of an open Ru{sub 3} triangle with four

  7. Ca cofactor of the water-oxidation complex: Evidence for a Mn/Ca heteronuclear cluster

    SciTech Connect

    Cinco, Roehl M.; Robblee, John H.; Messinger, Johannes; Fernandez, Carmen; McFarlane, Karen L.; Pizarro, Shelly A.; Sauer, Ken; Yachandra, Vittal K.

    2001-07-25

    Calcium and chloride are necessary cofactors for the proper function of the oxygen-evolving complex (OEC) of Photosystem II (PS II). Located in the thylakoid membranes of green plants, cyanobacteria and algae, PS II and the OEC catalyze the light-driven oxidation of water into dioxygen (released into the biosphere), protons and electrons for carbon fixation. The actual chemistry of water oxidation is performed by a cluster of four manganese atoms, along with the requisite cofactors Ca{sup 2+} and Cl{sup -}. While the Mn complex has been extensively studied by X-ray absorption techniques, comparatively less is known about the Ca{sup 2+} cofactor. The fewer number of studies on the Ca{sup 2+} cofactor have sometimes relied on substituting the native cofactor with strontium or other metals, and have stirred some debate about the structure of the binding site. past efforts using Mn EXAFS on Sr-substituted PSII are suggestive of a close link between the Mn cluster and Sr, within 3.5 {angstrom}. The most recent published study using Sr EXAFS on similar samples confirms this finding of a 3.5 {angstrom} distance between Mn and Sr. This finding was base3d on a second Fourier peak (R {approx} 3 {angstrom}) in the Sr EXAFS from functional samples, but is absent from inactive, hydroxylamine-treated PS II. This Fourier peak II was found to fit best to two Mn at 3.5 {angstrom} rather than lighter atoms (carbon). Nevertheless, other experiments have given contrary results. They wanted to extend the technique by using polarized Sr EXAFS on layered Sr-substituted samples, to provide important angle information. Polarized EXAFS involves collecting spectra for different incident angles ({theta}) between the membrane normal of the layered sample and the X-ray electric field vector. Dichroism in the EXAFS can occur, depending on how the particular absorber-backscatterer (A-B) vector is aligned with the electric field. Through analysis of the dichroism, they extract the average number

  8. The properties of clusters in the gas phase. IV - Complexes of H2O and HNOx clustering on NOx/-/

    NASA Technical Reports Server (NTRS)

    Lee, N.; Castleman, A. W., Jr.; Keesee, R. G.

    1980-01-01

    Thermodynamic quantities for the gas-phase clustering equilibria of NO2(-) and NO3(-) were determined with high-pressure mass spectrometry. A comparison of values of the free energy of hydration derived from the data shows good agreement with formerly reported values at 296 K. New data for larger NO2(-) and NO3(-) hydrates as well as NO2(-)(HNO2)n were obtained in this study. To aid in understanding the bonding and stability of the hydrates of nitrite and nitrate ions, CNDO/2 calculations were performed, and the results are discussed. A correlation between the aqueous-phase total hydration enthalpy of a single ion and its gas-phase hydration enthalpy was obtained. Atmospheric implications of the data are also briefly discussed.

  9. X-ray observations of complex temperature structure in the cool-core cluster A85

    SciTech Connect

    Schenck, David E.; Datta, Abhirup; Burns, Jack O.; Skillman, Sam

    2014-07-01

    X-ray observations were used to examine the complex temperature structure of A85, a cool-core galaxy cluster. Temperature features can provide evidence of merging events which shock heat the intracluster gas. Temperature maps were made from both Chandra and XMM-Newton observations. The combination of a new, long-exposure XMM observation and an improved temperature map binning technique produced the highest fidelity temperature maps of A85 to date. Hot regions were detected near the subclusters to the south and southwest in both the Chandra and XMM temperature maps. The presence of these structures implies A85 is not relaxed. The hot regions may indicate the presence of shocks. The Mach numbers were estimated to be ∼1.9 at the locations of the hot spots. Observational effects will tend to systematically reduce temperature jumps, so the measured Mach numbers are likely underestimated. Neither temperature map showed evidence for a shock in the vicinity of the presumed radio relic near the southwest subcluster. However, the presence of a weak shock cannot be ruled out. There was tension between the temperatures measured by the two instruments.

  10. Clustered regularly interspaced short palindromic repeats (CRISPRs) analysis of members of the Mycobacterium tuberculosis complex.

    PubMed

    Botelho, Ana; Canto, Ana; Leão, Célia; Cunha, Mónica V

    2015-01-01

    Typical CRISPR (clustered, regularly interspaced, short palindromic repeat) regions are constituted by short direct repeats (DRs), interspersed with similarly sized non-repetitive spacers, derived from transmissible genetic elements, acquired when the cell is challenged with foreign DNA. The analysis of the structure, in number and nature, of CRISPR spacers is a valuable tool for molecular typing since these loci are polymorphic among strains, originating characteristic signatures. The existence of CRISPR structures in the genome of the members of Mycobacterium tuberculosis complex (MTBC) enabled the development of a genotyping method, based on the analysis of the presence or absence of 43 oligonucleotide spacers separated by conserved DRs. This method, called spoligotyping, consists on PCR amplification of the DR chromosomal region and recognition after hybridization of the spacers that are present. The workflow beneath this methodology implies that the PCR products are brought onto a membrane containing synthetic oligonucleotides that have complementary sequences to the spacer sequences. Lack of hybridization of the PCR products to a specific oligonucleotide sequence indicates absence of the correspondent spacer sequence in the examined strain. Spoligotyping gained great notoriety as a robust identification and typing tool for members of MTBC, enabling multiple epidemiological studies on human and animal tuberculosis.

  11. Tribological coatings for complex mechanical elements produced by supersonic cluster beam deposition of metal dichalcogenide nanoparticles

    NASA Astrophysics Data System (ADS)

    Piazzoni, C.; Buttery, M.; Hampson, M. R.; Roberts, E. W.; Ducati, C.; Lenardi, C.; Cavaliere, F.; Piseri, P.; Milani, P.

    2015-07-01

    Fullerene-like MoS2 and WS2 nanoparticles can be used as building blocks for the fabrication of fluid and solid lubricants. Metal dichalcogenide films have a very low friction coefficient in vacuum, therefore they have mostly been used as solid lubricants in space and vacuum applications. Unfortunately, their use is significantly hampered by the fact that in the presence of humidity, oxygen and moisture, the low-friction properties of these materials rapidly degrade due to oxidation. The use of closed-cage MoS2 and WS2 nanoparticles may eliminate this problem, although the fabrication of lubricant thin films starting from dichalcogenide nanoparticles is, to date, a difficult task. Here we demonstrate the use of supersonic cluster beam deposition for the coating of complex mechanical elements (angular contact ball bearings) with nanostructured MoS2 and WS2 thin films. We report structural and tribological characterization of the coatings in view of the optimization of tribological performances for aerospace applications.

  12. Towards a methodology for cluster searching to provide conceptual and contextual “richness” for systematic reviews of complex interventions: case study (CLUSTER)

    PubMed Central

    2013-01-01

    Background Systematic review methodologies can be harnessed to help researchers to understand and explain how complex interventions may work. Typically, when reviewing complex interventions, a review team will seek to understand the theories that underpin an intervention and the specific context for that intervention. A single published report from a research project does not typically contain this required level of detail. A review team may find it more useful to examine a “study cluster”; a group of related papers that explore and explain various features of a single project and thus supply necessary detail relating to theory and/or context. We sought to conduct a preliminary investigation, from a single case study review, of techniques required to identify a cluster of related research reports, to document the yield from such methods, and to outline a systematic methodology for cluster searching. Methods In a systematic review of community engagement we identified a relevant project – the Gay Men’s Task Force. From a single “key pearl citation” we conducted a series of related searches to find contextually or theoretically proximate documents. We followed up Citations, traced Lead authors, identified Unpublished materials, searched Google Scholar, tracked Theories, undertook ancestry searching for Early examples and followed up Related projects (embodied in the CLUSTER mnemonic). Results Our structured, formalised procedure for cluster searching identified useful reports that are not typically identified from topic-based searches on bibliographic databases. Items previously rejected by an initial sift were subsequently found to inform our understanding of underpinning theory (for example Diffusion of Innovations Theory), context or both. Relevant material included book chapters, a Web-based process evaluation, and peer reviewed reports of projects sharing a common ancestry. We used these reports to understand the context for the intervention and to

  13. FRONTIER FIELDS CLUSTERS: DEEP CHANDRA OBSERVATIONS OF THE COMPLEX MERGER MACS J1149.6+2223

    SciTech Connect

    Ogrean, G. A.; Weeren, R. J. van; Jones, C.; Forman, W.; Andrade-Santos, F.; Murray, S. S.; Nulsen, P.; Bulbul, E.; Kraft, R.; Randall, S.; Dawson, W. A.; Golovich, N.; Roediger, E.; Zitrin, A.; Sayers, J.; Goulding, A.; Umetsu, K.; Mroczkowski, T.; Bonafede, A.; Churazov, E.; and others

    2016-03-10

    The Hubble Space Telescope Frontier Fields cluster MACS J1149.6+2223 is one of the most complex merging clusters, believed to consist of four dark matter halos. We present results from deep (365 ks) Chandra observations of the cluster, which reveal the most distant cold front (z  =  0.544) discovered to date. In the cluster outskirts, we also detect hints of a surface brightness edge that could be the bow shock preceding the cold front. The substructure analysis of the cluster identified several components with large relative radial velocities, thus indicating that at least some collisions occur almost along the line of sight. The inclination of the mergers with respect to the plane of the sky poses significant observational challenges at X-ray wavelengths. MACS J1149.6+2223 possibly hosts a steep-spectrum radio halo. If the steepness of the radio halo is confirmed, then the radio spectrum, combined with the relatively regular ICM morphology, could indicate that MACS J1149.6+2223 is an old merging cluster.

  14. Copper speciation in sulfidic solutions at low sulfur activity: Further evidence for cluster complexes?

    NASA Astrophysics Data System (ADS)

    Thompson, Richard A.; Helz, George R.

    1994-07-01

    The solubility of two as0-buffering assemblages in the Cu-S system have been studied: chalcocite-djurleite (Cc-Dj) and anilite-covellite (An-Cv). Ion activity products, [Cu +]HS -] 1/2[H +] - 1/2 (25°C, I = 0) at equilibrium, derived from solubility measurements in penicillamine solutions, are 10 -17.01 ± 0.05 (Cc-Dj) and 10 -17.14 ± 0.10 (An-Cv), from which ΔG° f = -82.11 kJ/mol for Cc and -74.77 kJ/mol for An. In the An-Cv assemblage, aCu2S = 0.55 (2 σ = 0.2) vs. 1.00 in the Cc-containing assemblage. The difference in aCu2S between the two assemblages is used in a novel way to estimate stoichiometry of Cu-HS complexes. The solubility of both assemblages (0.7-0.01 M NaHS, pH 7-12.5, 25°C) can be fit with a model incorporating the same two chemical species, one containing an odd number of Cu atoms (Cu(HS) 2-3, CU 3S 4H 2-3, or a higher multimer) and the other containing an even number of Cu atoms (Cu 2S(HS) 22-, Cu 4S 4H 22-, etc.). The trimer-tetramer model fits the combined data for the two assemblages distinctly better than the monomer-dimer model, but this result is very sensitive to uncertainty in aCu2S. Along with EXAFS results, the weight of the evidence favors small cluster complexes (2-5 Cu atoms), but is inconclusive at the present level of resolution. Multimers can be rationalized because condensation of metal-centered monomers to clusters provides a means for soft acid/base elements to maintain favored coordination geometries at low ligand to metal ratios. Based on the fitting methods developed here, previous covellite solubility data from this laboratory are reinterpreted in terms of Cu 2S 2(HS) 33-, Cu 2S 3)(S 4) 2-, and Cu(S 9)S 10) 3-; the last of these could also be represented by the trimer, Cu 3(S 7) 33-, which is homologous with a known complex. With the measured equilibrium constants, the speciation of Cu in the sulfidic zone of the Black Sea is calculated. Covellite is the stable Cu-S mineral, but the sulfidic water column is vastly

  15. Ring opening and carbonylation of 3,3-dimethylthietane ligands in ruthenium carbonyl cluster complexes

    SciTech Connect

    Adams, R.D.; Belinski, J.A.; Yamamoto, J.H.

    1992-10-01

    When heated to 97{degrees}C, the complex Ru{sub 4}(CO){sub 12}[{mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}]2 (1) was transformed into two new hexaruthenium cluster complexes, Ru{sub 6}(CO){sub 13}({mu}{sub 3}-SCH{sub 2}CMe{sub 2}CH{sub 2}){sub 4} (2) and Ru{sub 6}(CO){sub 12}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2})({mu}{sub 3}-SCH{sub 2}CMe{sub 2}CH{sub 2}){sub 3}[{mu}{sub 3}-SCH{sub 2}C(Me)(CH{sub 2})CH{sub 2}] ({mu}-H) (3), that contain four and five ring-opened 3,3-dimethylthietane (3,3-DMT) ligands, respectively. In compound 3 one of the ring-opened DMT ligands has also undergone a CH activation on one of the methyl groups. Compound 2 reacts with additional 3,3-DMT at 97{degrees}C to form 3 in 18% yield. When treated with CO at 95{degrees}C (500 psi), compound 2 yielded 4,4-dimethylthiobutyrolactone and Ru{sub 3}(CO){sub 12}. It was also found that the complex Os{sub 3}(CO){sub 11-}(SCH{sub 2}CMe{sub 2}CH{sub 2}C{double_bond}O) (4) yields 4,4-dimethylthiobutyrolactone when treated with CO at 120{degrees}C (1200 psi). Crystal data for 2: space group P2{sub 1}/n, {alpha} = 22.652 (7) A, {beta} = 11.712 (2) A, c = 19.965 (6) A, {Beta} = 115.75 (2){degrees} Z = 4, 3665 reflections, R = 0.021. Crystal data for 3: space group P2{sub 1}/c, {alpha} = 17.332 (8) A, {Beta} = 14.668 (9) A, c = 19.823 (9) A, {Beta} = 91.27 (4){degrees}, Z = 4, 1875 reflections, R = 0.050. 13 refs., 2 figs., 13 refs.

  16. Unusual structures and reactivity of mixed metal cluster complexes containing the palladium/platinum tri-t-butylphosphine grouping.

    PubMed

    Adams, Richard D; Captain, Burjor

    2009-03-17

    Polynuclear metal carbonyl complexes have a range of applications in chemical research: for example, they can serve as surface models to probe features of heterogeneous catalysis and can perform novel transformations of organic molecules in solutions. Mixed metal complexes can demonstrate bimetallic cooperativity and synergism and can also serve as precursors to multimetallic heterogeneous catalysts that have superior activities and selectivities. This Account describes the results of our recent comprehensive study of the chemistry of mixed metal cluster complexes containing the sterically encumbered M(PBu(t)(3)), M = Pd or Pt, group. This grouping readily adds to the metal-metal bonds of metal carbonyl cluster complexes and modifies their reactivity. We have prepared new, highly electronically unsaturated mixed metal complexes that exhibit unusually high reactivity toward hydrogen. The platinum atom of the Pt(PBu(t)(3)) grouping can bond to as many as five metal atoms, and it can interconvert, sometimes rapidly, between the different bonding modes. The large steric effects of the PBu(t)(3) ligand allowed us to prepare highly unsaturated, stable, mixed-metal complexes, and these complexes react with hydrogen, sometimes reversibly, under very mild conditions to yield polyhydride complexes. Strong evidence suggests that the Pt(PBu(t)(3)) group can also activate metal-hydrogen bonds in other complexes. In the future, we expect that researchers will prepare a greater variety of mixed metal complexes containing the Pd/Pt(PBu(t)(3)) group or other similar bulky groups, and that some of these complexes will exhibit even more unusual chemistry than what we have observed so far.

  17. Analysis of the Tribolium homeotic complex: insights into mechanisms constraining insect Hox clusters

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The remarkable conservation of Hox clusters is an accepted but little understood principle of biology. Some organizational constraints have been identified for vertebrate Hox clusters, but most of these are thought to be recent innovations that may not apply to other organisms. Ironically, many mode...

  18. Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

    SciTech Connect

    Krishnan Balasubramanian

    2009-07-18

    methods with all-electron Douglas-Kroll relativistic methods. We have the capabilities for computing full CI extrapolations including spin-orbit effects and several one-electron properties and electron density maps including spin-orbit effects. We are continuously collaborating with several experimental groups around the country and at National Labs to carry out computational studies on the DOE-BES funded projects. The past work in the last 3 years was primarily motivated and driven by the concurrent or recent experimental studies on these systems. We were thus significantly benefited by coordinating our computational efforts with experimental studies. The interaction between theory and experiment has resulted in some unique and exciting opportunities. For example, for the very first time ever, the upper spin-orbit component of a heavy trimer such as Au{sub 3} was experimentally observed as a result of our accurate computational study on the upper electronic states of gold trimer. Likewise for the first time AuH{sub 2} could be observed and interpreted clearly due to our computed potential energy surfaces that revealed the existence of a large barrier to convert the isolated AuH{sub 2} back to Au and H{sub 2}. We have also worked on yet to be observed systems and have made predictions for future experiments. We have computed the spectroscopic and thermodynamic properties of transition metal carbides transition metal clusters and compared our electronic states to the anion photodetachment spectra of Lai Sheng Wang. Prof Mike Morse and coworkers(funded also by DOE-BES) and Prof Stimle and coworkers(also funded by DOE-BES) are working on the spectroscopic properties of transition metal carbides and nitrides. Our predictions on the excited states of transition metal clusters such as Hf{sub 3}, Nb{sub 2}{sup +} etc., have been confirmed experimentally by Prof. Lombardi and coworkers using resonance Raman spectroscopy. We have also been studying larger complexes critical to the

  19. Modeling biological copper clusters: synthesis of a tricopper complex, and its chloride- and sulfide-bridged congeners.

    PubMed

    Di Francesco, Gianna N; Gaillard, Aleth; Ghiviriga, Ion; Abboud, Khalil A; Murray, Leslie J

    2014-05-05

    The synthesis and characterization of a family of tricopper clusters housed within a tris(β-diketimine) cyclophane ligand (H3L) that bear structural similarities to biological copper clusters are reported. In all complexes, each Cu atom is held within the N2-chelate of a single β-diketiminate arm. Reaction of L(3-) with CuCl affords an anionic complex containing a μ3-chloride donor in the central cavity, whereas there is no evidence for bromide incorporation in the product of the reaction of L(3-) with CuBr (Cu3L). Cu3L reacts with elemental sulfur to generate the corresponding air-stable mixed-valent (μ3-sulfido)tricopper complex, Cu3(μ3-S)L, which represents the first example of a sulfide-bridged copper cluster in which each metal center is both coordinatively unsaturated and held within a N-rich environment. The calculated LUMO is predominantly Cu-S π* in character and delocalized over all three metal centers, which is consistent with the isotropic ten-line absorption (g ∼ 2.095, A ∼ 33 G) observed at room temperature in EPR spectra of the one-electron chemically reduced complex, [Cu3(μ3-S)L](-).

  20. Anti-tumor and immunomodulatory activity of iron hepta-tungsten phosphate oxygen clusters complex.

    PubMed

    Zhang, Bisong; Qiu, Jianping; Wu, Changsheng; Li, Yunxia; Liu, Zhenxiang

    2015-12-01

    Polyoxometalates (POMs) have attracted a considerable attention due to their unique structural characteristics, physicochemical properties and biological activities. In this study, iron hepta-tungsten phosphate oxygen clusters complex Na12H[Fe(HPW7O28)2]·44H2O (IHTPO) was synthesized and evaluated for in vitro cytotoxic activities on human hepatoma HepG2, leukemia K562, lung carcinoma A549, and large cell lung cancer NCI-H460 cells, therapeutic efficacies on mice transplantable tumor, and immunomodulatory potentials on the immune response in tumor-bearing mice. IHTPO exhibited lower in vitro cytotoxic activities against four human tumor cell lines, with the IC50 values being higher than 62.5μM (ca. 300μg/ml). IHTPO, however, significantly inhibited the growth of S180 sarcoma transplanted in mice. It was further showed that IHTPO could not only significantly promote splenocytes proliferation, NK cell and CTL activity from splenocytes, but remarkably enhance serum antigen-specific IgG, IgG2a and IgG2b antibody levels in S180-bearing mice. IHTPO also significantly promoted Th1 cytokines IFN-γ and IL-2 production, and up-regulated the mRNA expression levels of IFN-γ, IL-2 and Th1 transcription factors T-bet and STAT-4 in splenocytes from the S180-bearing mice. These results suggested that IHTPO significantly inhibited the growth of mice transplantable tumor, and that its in vivo antitumor activity might be achieved by improving Th1 protective cell-mediated immunity. IHTPO could act as antitumor agent with immunomodulatory activity.

  1. Formation of supported rhodium clusters from mononuclear rhodium complexes controlled by the support and ligands on rhodium.

    PubMed

    Serna, Pedro; Yardimci, Dicle; Kistler, Joseph D; Gates, Bruce C

    2014-01-21

    Extremely small supported rhodium clusters were prepared from rhodium complexes on the surfaces of solids with contrasting electron-donor properties. The samples were characterized by infrared and extended X-ray absorption fine structure spectroscopies to determine the changes occurring in the rhodium species resulting from treatments in hydrogen. Rhodium cluster formation occurred in the presence of H2, and the first steps are controlled by the electron-donor properties of the support--which acts as a ligand--and the other ligands bonded to the rhodium. The cluster formation begins at a lower temperature when the support is zeolite HY than when it is the better electron-donor MgO, provided that the other ligands on rhodium are ethene. In contrast, when these other ligands are CO, the pattern is reversed. The choice of ligands including the support also allows regulation of the stoichiometry of the surface transformations in H2 and the stability of the structures formed in the presence of other reactants. The combination of MgO as the support and ethene as a ligand allows restriction of the rhodium cluster size to the smallest possible-and these were formed in high yields. The data presented here are among the first characterizing the first steps of metal cluster formation.

  2. Metal Sulfide Cluster Complexes and their Biogeochemical Importance in the Environment

    NASA Astrophysics Data System (ADS)

    Luther, George W.; Rickard, David T.

    2005-10-01

    Aqueous clusters of FeS, ZnS and CuS constitute a major fraction of the dissolved metal load in anoxic oceanic, sedimentary, freshwater and deep ocean vent environments. Their ubiquity explains how metals are transported in anoxic environmental systems. Thermodynamic and kinetic considerations show that they have high stability in oxic aqueous environments, and are also a significant fraction of the total metal load in oxic river waters. Molecular modeling indicates that the clusters are very similar to the basic structural elements of the first condensed phase forming from aqueous solutions in the Fe-S, Zn-S and Cu-S systems. The structure of the first condensed phase is determined by the structure of the cluster in solution. This provides an alternative explanation of Ostwald's Rule, where the most soluble, metastable phases form before the stable phases. For example, in the case of FeS, we showed that the first condensed phase is nanoparticulate, metastable mackinawite with a particle size of 2 nm consisting of about 150 FeS subunits, representing the end of a continuum between aqueous FeS clusters and condensed material. These metal sulfide clusters and nanoparticles are significant in biogeochemistry. Metal sulfide clusters reduce sulfide and metal toxicity and help drive ecology. FeS cluster formation drives vent ecology and AgS cluster formation detoxifies Ag in Daphnia magna neonates. We also note a new reaction between FeS and DNA and discuss the potential role of FeS clusters in denaturing DNA.

  3. Ligand/cluster/support catalytic complexes in heterogeneous ultrananocatalysis: NO oxidation on Ag3/MgO(100).

    PubMed

    Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Fortunelli, Alessandro

    2014-12-28

    In the present work we explore via first-principles simulations whether the ligand/cluster/support catalytic complex generated by CO oxidation over silver trimers deposited on the regular MgO(100) surface - i.e. a Ag3/carbonate or Ag3(CO3)/MgO(100) species - can be used as a catalyst in a different reaction: the selective oxidation of NO to NO2 (or NOox). The Ag3(CO3)/MgO(100) complex is first shown to be reasonably stable at room temperature in terms of both disaggregation and sintering, and that it can be generated from Ag3 adsorbed onto an oxygen vacancy defect of the regular MgO(100) surface under oxidation conditions. It is then found that the Ag3(CO3)/MgO(100) species transforms under NOox conditions into an even more complex aggregate, a mixed carbonate/double-nitrite Ag3(CO3)(NO2)2/MgO(100) species, which can then act as an efficient catalyst of NOox. It is noteworthy that under NOox reaction conditions a different ligand/cluster/support catalytic complex is formed with respect to the original COox one. These findings prove the diversity of the catalytic chemistry of subnanometer (or ultranano) metal clusters deposited on oxide substrates, associated with the formation of many different ligand/cluster/support aggregates, the vast amount of combinatorial possibilities thus opening, and the need for computational approaches to perform systematic structural and stoichiometric searches in order to cope with such a multiform diversity.

  4. The Complexities of Implementing Cluster Supply Chain - Case Study of JCH

    NASA Astrophysics Data System (ADS)

    Xue, Xiao; Zhang, Jibiao; Wang, Yang

    As a new type of management pattern, "cluster supply chain" (CSC) can help SMEs to face the global challenges through all kinds of collaboration. However, a major challenge in implementing CSC is the gap between theory and practice in the field. In an effort to provide a better understanding of this emerging phenomenon, this paper presents the implementation process of CSC in the context of JingCheng Mechanical & Electrical Holding co., ltd.(JCH) as a case study. The cast study of JCH suggests that the key problems in the practice of cluster supply chain: How do small firms use cluster supply chain? Only after we clarify the problem, the actual construction and operation of cluster supply chain does show successful results as it should be.

  5. The complex stellar populations in the background of open clusters in the third Galactic quadrant

    NASA Astrophysics Data System (ADS)

    Carraro, Giovanni; Seleznev, Anton F.; Baume, Gustavo; Turner, David. G.

    2016-02-01

    Multicolour photometry of the stellar populations in five fields in the third Galactic quadrant centred on the clusters NGC 2215, NGC 2354, Haffner 22, Ruprecht 11, and ESO489 SC01 is interpreted in terms of a warped and flared Galactic disc, without resort to an external entity such as the popular Monoceros or Canis Major overdensities. Except for NGC 2215, the clusters are poorly or unstudied previously. The data generate basic parameters for each cluster, including the distribution of stars along the line of sight. We use star counts and photometric analysis, without recourse to Galactic-model-based predictions or interpretations, and confirms earlier results for NGC 2215 and NGC 2354. ESO489 SC01 is not a real cluster, while Haffner 22 is an overlooked cluster aged ˜2.5 Gyr. Conclusions for Ruprecht 11 are preliminary, evidence for a cluster being marginal. Fields surrounding the clusters show signatures of young and intermediate-age stellar populations. The young population background to NGC 2354 and Ruprecht 11 lies ˜8-9 kpc from the Sun and ˜1 kpc below the formal Galactic plane, tracing a portion of the Norma-Cygnus arm, challenging Galactic models that adopt a sharp cut-off of the disc 12-14 kpc from the Galactic Centre. The old population is metal-poor with an age of ˜2-3 Gyr, resembling star clusters like Tombaugh 2 or NGC 2158. It has a large colour spread and is difficult to locate precisely. Young and old populations follow a pattern that depends critically on the vertical location of the thin and/or thick disc, and whether or not a particular line of sight intersects one, both, or none.

  6. Mössbauer Spectroscopy on Respiratory Complex I: The Iron–Sulfur Cluster Ensemble in the NADH-Reduced Enzyme Is Partially Oxidized

    PubMed Central

    2011-01-01

    In mitochondria, complex I (NADH:quinone oxidoreductase) couples electron transfer to proton translocation across an energy-transducing membrane. It contains a flavin mononucleotide to oxidize NADH, and an unusually long series of iron–sulfur (FeS) clusters that transfer the electrons to quinone. Understanding electron transfer in complex I requires spectroscopic and structural data to be combined to reveal the properties of individual clusters and of the ensemble. EPR studies on complex I from Bos taurus have established that five clusters (positions 1, 2, 3, 5, and 7 along the seven-cluster chain extending from the flavin) are (at least partially) reduced by NADH. The other three clusters, positions 4 and 6 plus a cluster on the other side of the flavin, are not observed in EPR spectra from the NADH-reduced enzyme: they may remain oxidized, have unusual or coupled spin states, or their EPR signals may be too fast relaxing. Here, we use Mössbauer spectroscopy on 57Fe-labeled complex I from the mitochondria of Yarrowia lipolytica to show that the cluster ensemble is only partially reduced in the NADH-reduced enzyme. The three EPR-silent clusters are oxidized, and only the terminal 4Fe cluster (position 7) is fully reduced. Together with the EPR analyses, our results reveal an alternating profile of higher and lower potential clusters between the two active sites in complex I; they are not consistent with the consensus picture of a set of isopotential clusters. The implications for intramolecular electron transfer along the extended chain of cofactors in complex I are discussed. PMID:22122402

  7. Formation of rhyolite at the Okataina Volcanic Complex, New Zealand: New insights from analysis of quartz clusters in plutonic lithics

    NASA Astrophysics Data System (ADS)

    Graeter, K.; Beane, R. J.; Deering, C. D.; Gravley, D. M.; Bachmann, O.

    2014-12-01

    Granitoid lithic clasts from the 0.7 ka Kaharoa eruption at the Tarawera volcano (Okataina Volcanic Complex, Taupo Volcanic Zone, New Zealand) - the world's most productive region where rhyolite volcanism is currently active - give insight into the processes of rhyolite formation. The plutonic lithic clasts of the Kaharoa eruption consist of (1) quartz phenocrysts, which are often grouped into clusters of two to eight quartz grains, (2) plagioclase phenocrysts with anorthitic cores and albitic rims, and (3) interstitial potassium feldspar. Quartz orientations obtained through electron backscatter diffraction (EBSD) methods show that 78% of the 82 analyzed clusters have at least one pair of quartz grains with matched dipyramidal faces that are in either parallel or Esterel twin orientation. Variations in cathodoluminescence (CL) zoning patterns of the quartz suggest that quartz clusters in the plutonic lithics formed after initial crystal growth and that many quartz crystals were subject to one or more resorption events. Thus, individual quartz crystals with different magmatic histories came together into preferred orientations to form clusters; this process is indicative of oriented quartz synneusis and suggests a history of crystal accumulation. The quartz clusters are interpreted to have formed as part of a crystal cumulate mush within a shallow magma chamber where quartz crystals rotated into contact along their dipyramidal faces during hindered settling and/or compaction. Therefore, the preservation of oriented quartz clusters from the Kaharoa plutonic lithics provides direct evidence for synchronous, shallow pluton formation from a cumulate mush during active volcanism. This result is consistent with a model whereby melt-rich, high-silica rhyolite formation occurs via interstitial melt extraction from a low-silica rhyolite mush in the shallow crust.

  8. Direct assignment of EPR spectra to structurally defined iron-sulfur clusters in complex I by double electron–electron resonance

    PubMed Central

    Roessler, Maxie M.; King, Martin S.; Robinson, Alan J.; Armstrong, Fraser A.; Harmer, Jeffrey; Hirst, Judy

    2010-01-01

    In oxidative phosphorylation, complex I (NADH:quinone oxidoreductase) couples electron transfer to proton translocation across an energy-transducing membrane. Complex I contains a flavin mononucleotide to oxidize NADH, and an unusually long series of iron-sulfur (FeS) clusters, in several subunits, to transfer the electrons to quinone. Understanding coupled electron transfer in complex I requires a detailed knowledge of the properties of individual clusters and of the cluster ensemble, and so it requires the correlation of spectroscopic and structural data: This has proved a challenging task. EPR studies on complex I from Bos taurus have established that EPR signals N1b, N2 and N3 arise, respectively, from the 2Fe cluster in the 75 kDa subunit, and from 4Fe clusters in the PSST and 51 kDa subunits (positions 2, 7, and 1 along the seven-cluster chain extending from the flavin). The other clusters have either evaded detection or definitive signal assignments have not been established. Here, we combine double electron-electron resonance (DEER) spectroscopy on B. taurus complex I with the structure of the hydrophilic domain of Thermus thermophilus complex I. By considering the magnetic moments of the clusters and the orientation selectivity of the DEER experiment explicitly, signal N4 is assigned to the first 4Fe cluster in the TYKY subunit (position 5), and N5 to the all-cysteine ligated 4Fe cluster in the 75 kDa subunit (position 3). The implications of our assignment for the mechanisms of electron transfer and energy transduction by complex I are discussed. PMID:20133838

  9. From thioxo cluster to dithio cluster: exploring the chemistry of polynuclear zirconium complexes with S,O and S,S ligands.

    PubMed

    Maratini, Federica; Pandolfo, Luciano; Bendova, Maria; Schubert, Ulrich; Bauer, Matthias; Rocchia, Massimiliano; Venzo, Alfonso; Tondello, Eugenio; Gross, Silvia

    2011-01-17

    Three different zirconium thio and oxothio clusters, characterized by different coordination modes of dithioacetate and/or monothioacetate ligands, were obtained by the reaction of monothioacetic acid with zirconium n-butoxide, Zr(O(n)Bu)4, in different experimental conditions. In particular, we isolated the three polynuclear Zr3(μ3-SSSCCH3)2(SSCCH3)6·2(n)BuOH (Zr3), Zr4(μ3-O)2(μ-η(1)-SOCCH3)2(SOCCH3)8(O(n)Bu)2 (Zr4), and Zr6(μ3-O)5(μ-SOCCH3)2(μ-OOCCH3)(SOCCH3)11((n)BuOH) (Zr6) derivatives, presenting some peculiar characteristics. Zr6 has an unusual star-shaped structure. Only sulfur-based ligands, viz., chelating dithioacetate monoanions and an unusual ethane-1,1,1-trithiolate group μ3 coordinating the Zr ions, were observed in the case of Zr3. 1D and 2D NMR analyses confirmed the presence of differently coordinated ligands. Raman spectroscopy was further used to characterize the new polynuclear complexes. Time-resolved extended X-ray absorption fine structure measurements, devoted to unraveling the cluster formation mechanisms, evidenced a fast coordination of sulfur ligands and subsequent relatively rapid rearrangements.

  10. Synthesis of a uranyl persulfide complex and quantum chemical studies of formation and topologies of hypothetical uranyl persulfide cage clusters.

    PubMed

    Grant, Daniel J; Weng, Zhehui; Jouffret, Laurent J; Burns, Peter C; Gagliardi, Laura

    2012-07-16

    The compound Na(4)[(UO(2))(S(2))(3)](CH(3)OH)(8) was synthesized at room temperature in an oxygen-free environment. It contains a rare example of the [(UO(2))(S(2))(3)](4-) complex in which a uranyl ion is coordinated by three bidentate persulfide groups. We examined the possible linkage of these units to form nanoscale cage clusters analogous to those formed from uranyl peroxide polyhedra. Quantum chemical calculations at the density functional and multiconfigurational wave function levels show that the uranyl-persulfide-uranyl, U-(S(2))-U, dihedral angles of model clusters are bent due to partial covalent interactions. We propose that this bent interaction will favor assembly of uranyl ions through persulfide bridges into curved structures, potentially similar to the family of nanoscale cage clusters built from uranyl peroxide polyhedra. However, the U-(S(2))-U dihedral angles predicted for several model structures may be too tight for them to self-assemble into cage clusters with fullerene topologies in the absence of other uranyl-ion bridges that adopt a flatter configuration. Assembly of species such as [(UO(2))(S(2))(SH)(4)](4-) or [(UO(2))(S(2))(C(2)O(4))(4)](4-) into fullerene topologies with ~60 vertices may be favored by use of large counterions.

  11. Cationic cluster formation versus disproportionation of low-valent indium and gallium complexes of 2,2'-bipyridine

    PubMed Central

    Lichtenthaler, Martin R.; Stahl, Florian; Kratzert, Daniel; Heidinger, Lorenz; Schleicher, Erik; Hamann, Julian; Himmel, Daniel; Weber, Stefan; Krossing, Ingo

    2015-01-01

    Group 13 MI compounds often disproportionate into M0 and MIII. Here, however, we show that the reaction of the MI salt of the weakly coordinating alkoxyaluminate [GaI(C6H5F)2]+[Al(ORF)4]− (RF=C(CF3)3) with 2,2'-bipyridine (bipy) yields the paramagnetic and distorted octahedral [Ga(bipy)3]2+•{[Al(ORF)4]−}2 complex salt. While the latter appears to be a GaII compound, both, EPR and DFT investigations assign a ligand-centred [GaIII{(bipy)3}•]2+ radical dication. Surprisingly, the application of the heavier homologue [InI(C6H5F)2]+[Al(ORF)4]− leads to aggregation and formation of the homonuclear cationic triangular and rhombic [In3(bipy)6]3+, [In3(bipy)5]3+ and [In4(bipy)6]4+ metal atom clusters. Typically, such clusters are formed under strongly reductive conditions. Analysing the unexpected redox-neutral cationic cluster formation, DFT studies suggest a stepwise formation of the clusters, possibly via their triplet state and further investigations attribute the overall driving force of the reactions to the strong In−In bonds and the high lattice enthalpies of the resultant ligand stabilized [M3]3+{[Al(ORF)4]−}3 and [M4]4+{[Al(ORF)4]−}4 salts. PMID:26478464

  12. Experiments in clustered neuronal networks: A paradigm for complex modular dynamics

    NASA Astrophysics Data System (ADS)

    Teller, Sara; Soriano, Jordi

    2016-06-01

    Uncovering the interplay activity-connectivity is one of the major challenges in neuroscience. To deepen in the understanding of how a neuronal circuit shapes network dynamics, neuronal cultures have emerged as remarkable systems given their accessibility and easy manipulation. An attractive configuration of these in vitro systems consists in an ensemble of interconnected clusters of neurons. Using calcium fluorescence imaging to monitor spontaneous activity in these clustered neuronal networks, we were able to draw functional maps and reveal their topological features. We also observed that these networks exhibit a hierarchical modular dynamics, in which clusters fire in small groups that shape characteristic communities in the network. The structure and stability of these communities is sensitive to chemical or physical action, and therefore their analysis may serve as a proxy for network health. Indeed, the combination of all these approaches is helping to develop models to quantify damage upon network degradation, with promising applications for the study of neurological disorders in vitro.

  13. {Ni4O4} Cluster Complex to Enhance the Reductive Photocurrent Response on Silicon Nanowire Photocathodes

    PubMed Central

    Mange, Yatin J.; Chandrasekaran, Soundarrajan; Hollingsworth, Nathan; Voelcker, Nicolas H.; Parkin, Ivan P.; Nann, Thomas; Macdonald, Thomas J.

    2017-01-01

    Metal organic {Ni4O4} clusters, known oxidation catalysts, have been shown to provide a valuable route in increasing the photocurrent response on silicon nanowire (SiNW) photocathodes. {Ni4O4} clusters have been paired with SiNWs to form a new photocathode composite for water splitting. Under AM1.5 conditions, the combination of {Ni4O4} clusters with SiNWs gave a current density of −16 mA/cm2, which corresponds to an increase in current density of 60% when compared to bare SiNWs. The composite electrode was fully characterised and shown to be an efficient and stable photocathode for water splitting. PMID:28336866

  14. Community detection in complex networks using density-based clustering algorithm and manifold learning

    NASA Astrophysics Data System (ADS)

    You, Tao; Cheng, Hui-Min; Ning, Yi-Zi; Shia, Ben-Chang; Zhang, Zhong-Yuan

    2016-12-01

    Like clustering analysis, community detection aims at assigning nodes in a network into different communities. Fdp is a recently proposed density-based clustering algorithm which does not need the number of clusters as prior input and the result is insensitive to its parameter. However, Fdp cannot be directly applied to community detection due to its inability to recognize the community centers in the network. To solve the problem, a new community detection method (named IsoFdp) is proposed in this paper. First, we use IsoMap technique to map the network data into a low dimensional manifold which can reveal diverse pair-wised similarity. Then Fdp is applied to detect the communities in the network. An improved partition density function is proposed to select the proper number of communities automatically. We test our method on both synthetic and real-world networks, and the results demonstrate the effectiveness of our algorithm over the state-of-the-art methods.

  15. Three complexes of Cu(I) cluster with flexible and rigid ligands: Synthesis, characterization and photoluminescent properties

    SciTech Connect

    Sun, Shu; Liu, Li-Juan; Ma, Wang-Yang; Zhou, Wei-Xia; Li, Jun; Zhang, Feng-Xing

    2015-05-15

    Three new Cu(I) cluster complexes, viz. [(Cu{sub 4}I{sub 4})(Cu{sub 2}I{sub 2})(dimb){sub 3}]{sub n} (1; dimb=1,4-diimidazol-1-ylbutane), [(Cu{sub 3}I{sub 2})(dimb)(dmtz)]{sub n} (2; dmtz=3,5-dimethyl-1,2,4-triazole), and [Cu{sub 6}(mbt){sub 6}] (3; mbt=2-mercaptobenzothiazole), have been solvothermally synthesized and structurally characterized. In 1, a Cu{sub 4}I{sub 4} cubane core as a 4-connecting node, connects the neighboring nodes either through single dimb or μ{sub 2}-[(Cu{sub 2}I{sub 2})(dimb){sub 2}] linkers, affording an undulated 2D (4,4) net. Parallel interpenetration occurs between the adjacent nets and thus the overall 2D→3D network is formed. Complex 2 is constructed by 2D (4,4) topological plane grid layers of AB stacking. The core, a distorted triangular bipyramidal Cu{sub 3}I{sub 2} cluster, is acted as a 4-connecting node and connected with dimb and μ{sub 3}-dmtz to form the layer. Complex 3 contains a (Cu{sub 6}S{sub 6}) core in discrete paddle-wheel molecule, which serves as a 4-connecting node to link equivalent ones via π···π interaction, forming 2D (4,4) layers. Solid-state luminescence properties and thermogravimetric analyses of 1, 2 and 3 were investigated. - Graphical abstract: Complexes based on Cu(I) clusters possess two-fold 2D→3D parallel interpenetrating (1), triple emissions (2) and near-infrared emission (3). - Highlights: • Complex 1 represents two-fold 2D→3D parallel interpenetrating framework. • Complex 2 shows triple emissions. • Complex 3 displays a quite intense near-infrared (NIR) emission. • These complexes have good thermal stability.

  16. Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of photosystem II.

    PubMed

    Cinco, Roehl M; McFarlane Holman, Karen L; Robblee, John H; Yano, Junko; Pizarro, Shelly A; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K

    2002-10-29

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared after Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 A, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is approximately 3.5 A distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

  17. Calcium EXAFS establishes the Mn-Ca cluster in the oxygen-evolving complex of Photosystem II

    SciTech Connect

    Cinco, Roehl M.; McFarlane Holman, Karen L.; Robblee, John H.; Yano, Junko; Pizarro, Shelly A.; Bellacchio, Emanuele; Sauer, Kenneth; Yachandra, Vittal K.

    2002-08-02

    The proximity of Ca to the Mn cluster of the photosynthetic water-oxidation complex is demonstrated by X-ray absorption spectroscopy. We have collected EXAFS data at the Ca K-edge using active PS II membrane samples that contain approximately 2 Ca per 4 Mn. These samples are much less perturbed than previously investigated Sr-substituted samples, which were prepared subsequent to Ca depletion. The new Ca EXAFS clearly shows backscattering from Mn at 3.4 angstroms, a distance that agrees with that surmised from previously recorded Mn EXAFS. This result is also consistent with earlier related experiments at the Sr K-edge, using samples that contained functional Sr, that show Mn is {approx}; 3.5 angstroms distant from Sr. The totality of the evidence clearly advances the notion that the catalytic center of oxygen evolution is a Mn-Ca heteronuclear cluster.

  18. Electrochemical anion sensing using electrodes chemically modified with Au(I)-Cu(I) heterotrimetallic alkynyl cluster complexes containing ferrocenyl groups.

    PubMed

    Doménech, Antonio; Koshevoy, Igor O; Montoya, Noemí; Pakkanen, Tapani A

    2010-07-01

    A novel family of electrochemical anion sensors operating in aqueous media, based on the heterometallic Au(I)-Cu(I) [{Au(3)Cu(2)(C(2)R)(6)}Au(3)(PPh(2)C(6)H(4)PPh(2))(3)](PF(6))(2) (L1, R = Fc; L2, R = C(6)H(4)Fc) alkynyl cluster complexes, is presented. Upon attachment to graphite and gold electrodes, these compounds exhibit a well-defined, essentially reversible, solid-state electrochemistry in contact with aqueous media, based on ferrocenyl-centered oxidation processes involving anion insertion, leading to distinctive pH-independent electrochemical responses for fluoride, chloride, bromide, perchlorate, bicarbonate, carbonate, phosphate, hydrogen phosphate, dihydrogen phosphate, and nitrate anions. Cluster-modified electrodes can be used as potentiometric sensors as a result of the reversible, diffusion-controlled electrochemistry obtained for the anion-assisted electrochemical oxidation of L1 and L2.

  19. Oligomeric rare-earth metal cluster complexes with endohedral transition metal atoms

    NASA Astrophysics Data System (ADS)

    Steinberg, Simon; Zimmermann, Sina; Brühmann, Matthias; Meyer, Eva; Rustige, Christian; Wolberg, Marike; Daub, Kathrin; Bell, Thomas; Meyer, Gerd

    2014-11-01

    Comproportionation reactions of rare-earth metal trihalides (RX3) with the respective rare-earth metals (R) and transition metals (T) led to the formation of 22 oligomeric R cluster halides encapsulating T, in 19 cases for the first time. The structures of these compounds were determined by single-crystal X-ray diffraction and are composed of trimers ({T3R11}X15-type, P63/m), tetramers ({T4R16}X28{R4} (P-43m), {T4R16}X20 (P42/nnm), {T4R16}X24(RX3)4 (I41/a) and {T4R16}X23 (C2/m) types of structure) and pentamers ({Ru5La14}2Br39, Cc) of {TRr}n (n=2-5) clusters. These oligomers are further enveloped by inner (Xi) as well as outer (Xa) halido ligands, which possess diverse functionalities and interconnect like oligomers through i-i, i-a and/or a-i bridges. The general features of the crystal structures for these new compounds are discussed and compared to literature entries as well as different structure types with oligomeric T centered R clusters. Dimers and tetramers originating from the aggregation of {TR6} octahedra via common edges are more frequent than trimers and pentamers, in which the {TRr} clusters share common faces.

  20. Multilevel Hierarchical Kernel Spectral Clustering for Real-Life Large Scale Complex Networks

    PubMed Central

    Mall, Raghvendra; Langone, Rocco; Suykens, Johan A. K.

    2014-01-01

    Kernel spectral clustering corresponds to a weighted kernel principal component analysis problem in a constrained optimization framework. The primal formulation leads to an eigen-decomposition of a centered Laplacian matrix at the dual level. The dual formulation allows to build a model on a representative subgraph of the large scale network in the training phase and the model parameters are estimated in the validation stage. The KSC model has a powerful out-of-sample extension property which allows cluster affiliation for the unseen nodes of the big data network. In this paper we exploit the structure of the projections in the eigenspace during the validation stage to automatically determine a set of increasing distance thresholds. We use these distance thresholds in the test phase to obtain multiple levels of hierarchy for the large scale network. The hierarchical structure in the network is determined in a bottom-up fashion. We empirically showcase that real-world networks have multilevel hierarchical organization which cannot be detected efficiently by several state-of-the-art large scale hierarchical community detection techniques like the Louvain, OSLOM and Infomap methods. We show that a major advantage of our proposed approach is the ability to locate good quality clusters at both the finer and coarser levels of hierarchy using internal cluster quality metrics on 7 real-life networks. PMID:24949877

  1. Complex Scattered Radiation Fields And Multiple Magnetic Fields In The Protostellar Cluster In NGC 2264

    NASA Astrophysics Data System (ADS)

    KWON, Jungmi; Tamura, M.; Kandori, R.; Kusakabe, N.; Hashimoto, J.; Nakajima, Y.; Nakamura, F.; Nagayama, T.; Nagata, T.; Hough, J. H.; Werner, M. W.; Teixeira, P. S.

    2012-05-01

    Near-infrared imaging polarimetry in the J, H, and Ks bands has been carried out for the protostellar cluster region around NGC 2264 IRS 2 in the Monoceros OB1 molecular cloud. Various infrared reflection nebula clusters (IRNCs) associated with NGC 2264 IRS 2 and the IRAS 12 S1 core, as well as local infrared reflection nebulae (IRNe), were detected. The illuminating sources of the IRNe were identified with known or new near- and mid-infrared sources. In addition, 314 point-like sources were detected in all three bands and their aperture polarimetry was studied. Using a color-color diagram, reddened field stars and diskless pre-main-sequence stars were selected to trace the magnetic field structure of the molecular cloud. The mean polarization position angle of the point-like sources is 80 degrees in the cluster core, and 60 degrees in the perimeter of the cluster core, which is interpreted as the projected direction on the sky of the magnetic field in the observed region of the cloud. The Chandrasekhar-Fermi method gives a rough estimate of the magnetic field strength to be about 100 micro-Gauss. A comparison with recent numerical simulations of the cluster formation implies that the cloud dynamics is controlled by the relatively strong magnetic field. The local magnetic field direction is well associated with that of CO outflow for IRAS 12 S1 and consistent with that inferred from submillimeter polarimetry. In contrast, the local magnetic field direction runs roughly perpendicular to the Galactic magnetic field direction.

  2. Complex Scattered Radiation Fields and Multiple Magnetic Fields in the Protostellar Cluster in NGC 2264

    NASA Astrophysics Data System (ADS)

    Kwon, Jungmi; Tamura, Motohide; Kandori, Ryo; Kusakabe, Nobuhiko; Hashimoto, Jun; Nakajima, Yasushi; Nakamura, Fumitaka; Nagayama, Takahiro; Nagata, Tetsuya; Hough, James H.; Werner, Michael W.; Teixeira, Paula S.

    2011-11-01

    Near-infrared imaging polarimetry in the J, H, and Ks bands has been carried out for the protostellar cluster region around NGC 2264 IRS 2 in the Monoceros OB1 molecular cloud. Various infrared reflection nebula clusters (IRNCs) associated with NGC 2264 IRS 2 and the IRAS 12 S1 core, as well as local infrared reflection nebulae (IRNe), were detected. The illuminating sources of the IRNe were identified with known or new near- and mid-infrared sources. In addition, 314 point-like sources were detected in all three bands and their aperture polarimetry was studied. Using a color-color diagram, reddened field stars and diskless pre-main-sequence stars were selected to trace the magnetic field (MF) structure of the molecular cloud. The mean polarization position angle of the point-like sources is 81° ± 29° in the cluster core, and 58° ± 24° in the perimeter of the cluster core, which is interpreted as the projected direction on the sky of the MF in the observed region of the cloud. The Chandrasekhar-Fermi method gives a rough estimate of the MF strength to be about 100 μG. A comparison with recent numerical simulations of the cluster formation implies that the cloud dynamics is controlled by the relatively strong MF. The local MF direction is well associated with that of CO outflow for IRAS 12 S1 and consistent with that inferred from submillimeter polarimetry. In contrast, the local MF direction runs roughly perpendicular to the Galactic MF direction.

  3. Three complexes of Cu(I) cluster with flexible and rigid ligands: Synthesis, characterization and photoluminescent properties

    NASA Astrophysics Data System (ADS)

    Sun, Shu; Liu, Li-Juan; Ma, Wang-Yang; Zhou, Wei-Xia; Li, Jun; Zhang, Feng-Xing

    2015-05-01

    Three new Cu(I) cluster complexes, viz. [(Cu4I4)(Cu2I2)(dimb)3]n (1; dimb=1,4-diimidazol-1-ylbutane), [(Cu3I2)(dimb)(dmtz)]n (2; dmtz=3,5-dimethyl-1,2,4-triazole), and [Cu6(mbt)6] (3; mbt=2-mercaptobenzothiazole), have been solvothermally synthesized and structurally characterized. In 1, a Cu4I4 cubane core as a 4-connecting node, connects the neighboring nodes either through single dimb or μ2-[(Cu2I2)(dimb)2] linkers, affording an undulated 2D (4,4) net. Parallel interpenetration occurs between the adjacent nets and thus the overall 2D→3D network is formed. Complex 2 is constructed by 2D (4,4) topological plane grid layers of AB stacking. The core, a distorted triangular bipyramidal Cu3I2 cluster, is acted as a 4-connecting node and connected with dimb and μ3-dmtz to form the layer. Complex 3 contains a (Cu6S6) core in discrete paddle-wheel molecule, which serves as a 4-connecting node to link equivalent ones via π···π interaction, forming 2D (4,4) layers. Solid-state luminescence properties and thermogravimetric analyses of 1, 2 and 3 were investigated.

  4. UV Insights into the Complex Populations of M87 Globular Clusters

    NASA Astrophysics Data System (ADS)

    Bellini, A.; Renzini, A.; Anderson, J.; Bedin, L. R.; Piotto, G.; Soto, M.; Brown, T. M.; Milone, A. P.; Sohn, S. T.; Sweigart, A. V.

    2015-06-01

    We have imaged with Hubble Space Telescope WFC3/UVIS the central 2\\buildrel{ \\prime}\\over{.} 7× 2\\buildrel{ \\prime}\\over{.} 7 region of the giant elliptical galaxy M87, using the ultraviolet filter F275W. In combination with archival ACS/WFC data taken through the F606W and F814W filters, covering the same field, we have constructed integrated-light UV-optical colors and magnitudes for 1460 objects, most of which are believed to be globular clusters (GCs) belonging to M87. The purpose was to ascertain whether the multiple-populations syndrome, ubiquitous among Galactic GCs, also exists among the M87 family of clusters. To achieve this goal, we sought those GCs with exceptionally blue UV-to-optical colors because helium-enriched sub-populations produce a horizontal-branch morphology that is well populated at high effective temperature. For comparison, integrated, synthetic UV-optical and purely optical colors and magnitudes have been constructed for 45 Galactic GCs, starting from individual-star photometry obtained with the same instruments and the same filters. We identify a small group of M87 clusters exhibiting a radial UV-optical color gradient, representing our best candidate GCs hosting multiple populations with extreme helium content. We also find that the central spatial distribution of the bluer GCs is flattened in a direction parallel to the jet, while the distribution of redder GCs is more spherical. We release to the astronomical community our photometric catalog in F275W, F606W, and F814W bands and the high-quality image stacks in the same bands. Based on proprietary and archival observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by AURA, Inc., under NASA contract NAS 5-26555.

  5. Toward accurate molecular identification of species in complex environmental samples: testing the performance of sequence filtering and clustering methods

    PubMed Central

    Flynn, Jullien M; Brown, Emily A; Chain, Frédéric J J; MacIsaac, Hugh J; Cristescu, Melania E

    2015-01-01

    Metabarcoding has the potential to become a rapid, sensitive, and effective approach for identifying species in complex environmental samples. Accurate molecular identification of species depends on the ability to generate operational taxonomic units (OTUs) that correspond to biological species. Due to the sometimes enormous estimates of biodiversity using this method, there is a great need to test the efficacy of data analysis methods used to derive OTUs. Here, we evaluate the performance of various methods for clustering length variable 18S amplicons from complex samples into OTUs using a mock community and a natural community of zooplankton species. We compare analytic procedures consisting of a combination of (1) stringent and relaxed data filtering, (2) singleton sequences included and removed, (3) three commonly used clustering algorithms (mothur, UCLUST, and UPARSE), and (4) three methods of treating alignment gaps when calculating sequence divergence. Depending on the combination of methods used, the number of OTUs varied by nearly two orders of magnitude for the mock community (60–5068 OTUs) and three orders of magnitude for the natural community (22–22191 OTUs). The use of relaxed filtering and the inclusion of singletons greatly inflated OTU numbers without increasing the ability to recover species. Our results also suggest that the method used to treat gaps when calculating sequence divergence can have a great impact on the number of OTUs. Our findings are particularly relevant to studies that cover taxonomically diverse species and employ markers such as rRNA genes in which length variation is extensive. PMID:26078860

  6. Mono- and bimetallic manganese-carbonyl complexes and clusters bearing imidazol(in)ium-2-dithiocarboxylate ligands.

    PubMed

    Beltrán, Tomás F; Zaragoza, Guillermo; Delaude, Lionel

    2017-02-14

    Five complexes with the generic formula fac-[MnBr(CO)3(S2C·NHC)] were obtained by reacting [MnBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The mononuclear Mn(i) derivatives were coupled with Na[Mn(CO)5] to afford bimetallic [Mn2(CO)6(S2C·NHC)] clusters. Yet, the most convenient strategy to access these dinuclear Mn(0) products implied a direct carbonyl substitution from the [Mn2(CO)10] dimer. The molecular structures of three monometallic and four bimetallic compounds were elucidated by single crystal X-ray diffraction analysis. In the monometallic complexes, the NHC·CS2 ligands exhibited a bidentate κ(2)-S,S' coordination mode with an S-C-S bite angle of about 116°. In the dinuclear clusters, the CS2(-) unit acted as a chelate toward one manganese center and as a pseudoallylic ligand toward the other one. The S-C-S bite angle was reduced to ca. 104°. Thus, the zwitterions displayed a remarkable flexibility, which also permitted a staggered arrangement of the carbonyl groups in the bimetallic systems. Examination of the [small nu, Greek, macron]CO absorption bands on IR spectroscopy helped identify the presence of fac-Mn(CO)3 or Mn2(CO)6 motifs, while the (13)C NMR chemical shift of the CS2(-) moiety was a reliable indicator for monitoring its hapticity. Whereas the dinuclear clusters were air- and moisture-stable crystalline solids, mononuclear halido derivatives displayed only a limited stability under aerobic conditions. Both types of compounds underwent rather unselective, extensive fragmentations in the gas phase, in sharp contrast with the analogous rhenium derivatives that led to clean sequential decarbonylation processes upon collision-induced dissociation.

  7. Electronic Structure of Transition Metal Clusters and Actinide Complexes and Their Reactivity

    SciTech Connect

    Balasubramanian, K

    2008-10-06

    Our research in this area since October 2007 has resulted in seven completed publications and more papers of the completed work are in progress. Our work during this period principally focused on actinide complexes with secondary emphasis on spectroscopic properties and electronic structure of metal complexes. As the publications are available online with all of the details of the results, tables and figures, we are providing here only a brief summary of major highlights, in each of the categories.

  8. Clustered coding variants in the glutamate receptor complexes of individuals with schizophrenia and bipolar disorder.

    PubMed

    Frank, René A W; McRae, Allan F; Pocklington, Andrew J; van de Lagemaat, Louie N; Navarro, Pau; Croning, Mike D R; Komiyama, Noboru H; Bradley, Sophie J; Challiss, R A John; Armstrong, J Douglas; Finn, Robert D; Malloy, Mary P; MacLean, Alan W; Harris, Sarah E; Starr, John M; Bhaskar, Sanjeev S; Howard, Eleanor K; Hunt, Sarah E; Coffey, Alison J; Ranganath, Venkatesh; Deloukas, Panos; Rogers, Jane; Muir, Walter J; Deary, Ian J; Blackwood, Douglas H; Visscher, Peter M; Grant, Seth G N

    2011-04-29

    Current models of schizophrenia and bipolar disorder implicate multiple genes, however their biological relationships remain elusive. To test the genetic role of glutamate receptors and their interacting scaffold proteins, the exons of ten glutamatergic 'hub' genes in 1304 individuals were re-sequenced in case and control samples. No significant difference in the overall number of non-synonymous single nucleotide polymorphisms (nsSNPs) was observed between cases and controls. However, cluster analysis of nsSNPs identified two exons encoding the cysteine-rich domain and first transmembrane helix of GRM1 as a risk locus with five mutations highly enriched within these domains. A new splice variant lacking the transmembrane GPCR domain of GRM1 was discovered in the human brain and the GRM1 mutation cluster could perturb the regulation of this variant. The predicted effect on individuals harbouring multiple mutations distributed in their ten hub genes was also examined. Diseased individuals possessed an increased load of deleteriousness from multiple concurrent rare and common coding variants. Together, these data suggest a disease model in which the interplay of compound genetic coding variants, distributed among glutamate receptors and their interacting proteins, contribute to the pathogenesis of schizophrenia and bipolar disorders.

  9. Communication: Relativistic Fock-space coupled cluster study of small building blocks of larger uranium complexes

    SciTech Connect

    Tecmer, Paweł Visscher, Lucas; Severo Pereira Gomes, André; Knecht, Stefan

    2014-07-28

    We present a study of the electronic structure of the [UO{sub 2}]{sup +}, [UO{sub 2}]{sup 2} {sup +}, [UO{sub 2}]{sup 3} {sup +}, NUO, [NUO]{sup +}, [NUO]{sup 2} {sup +}, [NUN]{sup −}, NUN, and [NUN]{sup +} molecules with the intermediate Hamiltonian Fock-space coupled cluster method. The accuracy of mean-field approaches based on the eXact-2-Component Hamiltonian to incorporate spin–orbit coupling and Gaunt interactions are compared to results obtained with the Dirac–Coulomb Hamiltonian. Furthermore, we assess the reliability of calculations employing approximate density functionals in describing electronic spectra and quantities useful in rationalizing Uranium (VI) species reactivity (hardness, electronegativity, and electrophilicity)

  10. Iridium Complexes and Clusters in Dealuminated Zeolite HY: Distribution between Crystalline and Impurity Amorphous Regions

    SciTech Connect

    Martinez-Macias, Claudia; Xu, Pinghong; Hwang, Son-Jong; Lu, Jing; Chen, Cong-Yan; Browning, Nigel D.; Gates, Bruce C.

    2014-07-08

    Dealuminated zeolite HY was used to support Ir(CO)2 complexes formed from Ir(CO)2(C5H7O2). Infrared and X-ray absorption spectra and atomic-resolution electron microscopy images identify these complexes, and the images and 27Al NMR spectra identify impurity amorphous regions in the zeolite where the iridium is more susceptible to aggregation than in the crystalline regions. The results indicate a significant stability limitation of metal in amorphous impurity regions of zeolites.

  11. Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

    PubMed Central

    Liu, Siqi; Xu, Yi-Jun

    2016-01-01

    The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability. PMID:26947754

  12. Characterization of Toxin Complex Gene Clusters and Insect Toxicity of Bacteria Representing Four Subgroups of Pseudomonas fluorescens

    PubMed Central

    Rangel, Lorena I.; Henkels, Marcella D.; Shaffer, Brenda T.; Walker, Francesca L.; Davis, Edward W.; Stockwell, Virginia O.; Bruck, Denny; Taylor, Barbara J.; Loper, Joyce E.

    2016-01-01

    Ten strains representing four lineages of the Pseudomonas fluorescens group (P. chlororaphis, P. corrugata, P. koreensis, and P. fluorescens subgroups) were evaluated for toxicity to the tobacco hornworm Manduca sexta and the common fruit fly Drosophila melanogaster. The three strains within the P. chlororaphis subgroup exhibited both oral and injectable toxicity to the lepidopteran M. sexta. All three strains have the gene cluster encoding the FitD insect toxin and a ΔfitD mutant of P. protegens strain Pf-5 exhibited diminished oral toxicity compared to the wildtype strain. Only one of the three strains, P. protegens Pf-5, exhibited substantial levels of oral toxicity against the dipteran D. melanogaster. Three strains in the P. fluorescens subgroup, which lack fitD, consistently showed significant levels of injectable toxicity against M. sexta. In contrast, the oral toxicity of these strains against D. melanogaster was variable between experiments, with only one strain, Pseudomonas sp. BG33R, causing significant levels of mortality in repeated experiments. Toxin complex (Tc) gene clusters, which encode insecticidal properties in Photorhabdus luminescens, were identified in the genomes of seven of the ten strains evaluated in this study. Within those seven genomes, six types of Tc gene clusters were identified, distinguished by gene content, organization and genomic location, but no correlation was observed between the presence of Tc genes and insect toxicity of the evaluated strains. Our results demonstrate that members of the P. fluorescens group have the capacity to kill insects by both FitD-dependent and independent mechanisms. PMID:27580176

  13. Excited State Energetics and Dynamics of Large Molecules, Complexes and Clusters

    DTIC Science & Technology

    1988-07-01

    States of Large Molecules 6 .4,,4 7- - . / ,-° - . . - ii - Page No. 7. (cont’d) K) Photoisomerization Dynamics of Trans- Stilbene and 6 of Cis- Stilbene L...Photoisomerization Dynamics of Alkyl Substituted Trans- Stilbene 6 M) Energy-Resolved Photoisomerization Rates 7 N) van der Waals Complexes and... Stilbene andof CisStilbene. Time-resolved fluorescence lifetimes from photoselected states of trans- stilbene were recorded by the techniques of

  14. The C-type lectin-like receptors of Dectin-1 cluster in natural killer gene complex.

    PubMed

    Xie, Jianhui

    2012-08-01

    Natural killer gene complex (NKC) encodes a group of proteins with a single C-type lectin-like domain, (CTLD) which can be subdivided several subfamilies according to their structures and expression patterns. The receptors containing the conserved calcium binding sites in the CTLD fold belong to group II of C-type lectin superfamily and are expressed on myeloid cells and non- myeloid cells. The receptors lacking conserved calcium binding sites in the CTLD fold have evolved to bind ligands other than carbohydrates independently on calcium and thereby are named as C-type lectin-like receptors. The C-type lectin-like receptors are previously thought to be exclusively expressed on natural killer (NK) cells and enable NK cells to discriminate self, missing self or altered self. However, some C-type lectin-like receptors are identified in myeloid cells and are intensely investigated, recently. These myeloid C-type lectin-like receptors, especially Dectin-1 cluster, have a wide variety of ligands, including those of exogenous origin, and play important roles in the physiological functions and pathological processes including immune homeostasis, immune defenses, and immune surveillance. In this review, we summarize each member of the Dectin-1 cluster, including their structural profiles, expression patterns, signaling properties as well as known physiological functions.

  15. Quick detection of QRS complexes and R-waves using a wavelet transform and K-means clustering.

    PubMed

    Xia, Yong; Han, Junze; Wang, Kuanquan

    2015-01-01

    Based on the idea of telemedicine, 24-hour uninterrupted monitoring on electrocardiograms (ECG) has started to be implemented. To create an intelligent ECG monitoring system, an efficient and quick detection algorithm for the characteristic waveforms is needed. This paper aims to give a quick and effective method for detecting QRS-complexes and R-waves in ECGs. The real ECG signal from the MIT-BIH Arrhythmia Database is used for the performance evaluation. The method proposed combined a wavelet transform and the K-means clustering algorithm. A wavelet transform is adopted in the data analysis and preprocessing. Then, based on the slope information of the filtered data, a segmented K-means clustering method is adopted to detect the QRS region. Detection of the R-peak is based on comparing the local amplitudes in each QRS region, which is different from other approaches, and the time cost of R-wave detection is reduced. Of the tested 8 records (total 18201 beats) from the MIT-BIH Arrhythmia Database, an average R-peak detection sensitivity of 99.72 and a positive predictive value of 99.80% are gained; the average time consumed detecting a 30-min original signal is 5.78s, which is competitive with other methods.

  16. Synthesis and structural characterization of bimetallic iron-nickel carbido cluster complexes.

    PubMed

    Saha, Sumit; Zhu, Lei; Captain, Burjor

    2010-04-05

    In acetonitrile solvent, Fe(5)(CO)(15)(mu(5)-C), 1, reacts with Ni(COD)(2) at room temperature to afford the iron-nickel complex Fe(5)Ni(NCMe)(CO)(15)(mu(6)-C), 3. The acetonitrile ligand in 3 can be replaced by CO and NH(3) to yield Fe(5)Ni(CO)(16)(mu(6)-C), 4, and Fe(5)Ni(NH(3))(CO)(15)(mu(6)-C), 6, respectively. When refluxed in acetonitrile solvent, compound 3 loses a vertex to form the square pyramidal Fe(4)Ni complex Fe(4)Ni(NCMe)(2)(CO)(12)(mu(5)-C), 7. Compound 7 readily converts to Fe(4)Ni(NCMe)(CO)(13)(mu(5)-C), 8, by losing one of its acetonitrile ligands. Addition of acetonitrile to 8 gives compound 7. When heated to 110 degrees C under an atmosphere of CO, both compounds 7 and 8 furnish the octahedral Fe(4)Ni(2) complex Fe(4)Ni(2)(CO)(15)(mu(6)-C), 9. All six compounds were structurally characterized by single-crystal X-ray diffraction analyses.

  17. Crystal Structures of the Iron–Sulfur Cluster-Dependent Quinolinate Synthase in Complex with Dihydroxyacetone Phosphate, Iminoaspartate Analogues, and Quinolinate

    SciTech Connect

    Fenwick, Michael K.; Ealick, Steven E.

    2016-07-12

    The quinolinate synthase of prokaryotes and photosynthetic eukaryotes, NadA, contains a [4Fe-4S] cluster with unknown function. We report crystal structures of Pyrococcus horikoshii NadA in complex with dihydroxyacetone phosphate (DHAP), iminoaspartate analogues, and quinolinate. DHAP adopts a nearly planar conformation and chelates the [4Fe-4S] cluster via its keto and hydroxyl groups. The active site architecture suggests that the cluster acts as a Lewis acid in enediolate formation, like zinc in class II aldolases. The DHAP and putative iminoaspartate structures suggest a model for a condensed intermediate. The ensemble of structures suggests a two-state system, which may be exploited in early steps.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  19. Implementing a Complex Intervention to Support Personal Recovery: A Qualitative Study Nested within a Cluster Randomised Controlled Trial

    PubMed Central

    Leamy, Mary; Clarke, Eleanor; Le Boutillier, Clair; Bird, Victoria; Janosik, Monika; Sabas, Kai; Riley, Genevieve; Williams, Julie; Slade, Mike

    2014-01-01

    Objective To investigate staff and trainer perspectives on the barriers and facilitators to implementing a complex intervention to help staff support the recovery of service users with a primary diagnosis of psychosis in community mental health teams. Design Process evaluation nested within a cluster randomised controlled trial (RCT). Participants 28 interviews with mental health care staff, 3 interviews with trainers, 4 focus groups with intervention teams and 28 written trainer reports. Setting 14 community-based mental health teams in two UK sites (one urban, one semi-rural) who received the intervention. Results The factors influencing the implementation of the intervention can be organised under two over-arching themes: Organisational readiness for change and Training effectiveness. Organisational readiness for change comprised three sub-themes: NHS Trust readiness; Team readiness; and Practitioner readiness. Training effectiveness comprised three sub-themes: Engagement strategies; Delivery style and Modelling recovery principles. Conclusions Three findings can inform future implementation and evaluation of complex interventions. First, the underlying intervention model predicted that three areas would be important for changing practice: staff skill development; intention to implement; and actual implementation behaviour. This study highlighted the importance of targeting the transition from practitioners' intent to implement to actual implementation behaviour, using experiential learning and target setting. Second, practitioners make inferences about organisational commitment by observing the allocation of resources, Knowledge Performance Indicators and service evaluation outcome measures. These need to be aligned with recovery values, principles and practice. Finally, we recommend the use of organisational readiness tools as an inclusion criteria for selecting both organisations and teams in cluster RCTs. We believe this would maximise the likelihood of

  20. The connection between prestellar cores and filaments in cluster-forming clumps of the Aquila Rift complex

    NASA Astrophysics Data System (ADS)

    Könyves, Vera; André, Philippe; Maury, Anaëlle

    2015-08-01

    One of the main goals of the Herschel Gould Belt survey (André et al. 2010) is to elucidate the physicalmechanisms responsible for the formation and evolution of prestellar cores in molecular clouds. In theAquila cloud complex imaged with Herschel/SPIRE-PACS between 70-500 μm, we have recently identifieda complete sample of 651 starless cores, 446 of them are gravitationally-bound prestellar cores, likelyforming stars in the future. We also detected 58 protostellar cores (Könyves et al. 2010 and 2015, subm.- see http://gouldbelt-herschel.cea.fr/archives). This region is dominated by two (proto)clusters which arecurrently active sites of clustered star formation (SF): the filamentary Serpens South cloud and the W40HII region. The latter is powered by massive young stars, and a 2nd-generation SF can be witnessed inthe surroundings (Maury et al. 2011).Our Herschel observations also provide an unprecedented census of filaments in Aquila and suggest aclose connection between them and the formation process of prestellar cores, where both structures arehighly concentrated around the protoclusters. About 10-20% of the gas mass is in the form of filamentsbelow Av~7, while ~50-75% of the dense gas mass above Av~7-10 is in filamentary structures.Furthermore, ~90% of our prestellar cores are located above a background column density correspondingto Av~7, and ~75% of them lie within the densest filamentary structures with supercritical masses per unitlength >16 M⊙/pc. Indeed, a strong correlation is found between the spatial distribution of prestellar coresand the densest filaments.Comparing the statistics of cores and filaments with the number of young stellar objects found by Spitzerin the same complex, we also infer a typical timescale ~1 Myr for the formation and evolution of bothprestellar cores and filaments.In summary, our Herschel findings in Aquila support a filamentary paradigm for the early stages of SF,where the cores result from the gravitational fragmentation

  1. Synaptonemal complex extension from clustered telomeres mediates full-length chromosome pairing in Schmidtea mediterranea

    PubMed Central

    Xiang, Youbin; Miller, Danny E.; Ross, Eric J.; Sánchez Alvarado, Alejandro; Hawley, R. Scott

    2014-01-01

    In the 1920s, József Gelei proposed that chromosome pairing in flatworms resulted from the formation of a telomere bouquet followed by the extension of synapsis from telomeres at the base of the bouquet, thus facilitating homolog pairing in a processive manner. A modern interpretation of Gelei’s model postulates that the synaptonemal complex (SC) is nucleated close to the telomeres and then extends progressively along the full length of chromosome arms. We used the easily visible meiotic chromosomes, a well-characterized genome, and RNAi in the sexual biotype of the planarian Schmidtea mediterranea to test that hypothesis. By identifying and characterizing S. mediterranea homologs of genes encoding synaptonemal complex protein 1 (SYCP1), the topoisomerase-like protein SPO11, and RAD51, a key player in homologous recombination, we confirmed that SC formation begins near the telomeres and progresses along chromosome arms during zygotene. Although distal regions pair at the time of bouquet formation, pairing of a unique interstitial locus is not observed until the formation of full-length SC at pachytene. Moreover, neither full extension of the SC nor homologous pairing is dependent on the formation of double-strand breaks. These findings validate Gelei’s speculation that full-length pairing of homologous chromosomes is mediated by the extension of the SC formed near the telomeres. S. mediterranea thus becomes the first organism described (to our knowledge) that forms a canonical telomere bouquet but does not require double-strand breaks for synapsis between homologous chromosomes. However, the initiation of SC formation at the base of the telomere bouquet, which then is followed by full-length homologous pairing in planarian spermatocytes, is not observed in other species and may not be conserved. PMID:25404302

  2. A CEP215–HSET complex links centrosomes with spindle poles and drives centrosome clustering in cancer

    PubMed Central

    Chavali, Pavithra L.; Chandrasekaran, Gayathri; Barr, Alexis R.; Tátrai, Péter; Taylor, Chris; Papachristou, Evaggelia K.; Woods, C. Geoffrey; Chavali, Sreenivas; Gergely, Fanni

    2016-01-01

    Numerical centrosome aberrations underlie certain developmental abnormalities and may promote cancer. A cell maintains normal centrosome numbers by coupling centrosome duplication with segregation, which is achieved through sustained association of each centrosome with a mitotic spindle pole. Although the microcephaly- and primordial dwarfism-linked centrosomal protein CEP215 has been implicated in this process, the molecular mechanism responsible remains unclear. Here, using proteomic profiling, we identify the minus end-directed microtubule motor protein HSET as a direct binding partner of CEP215. Targeted deletion of the HSET-binding domain of CEP215 in vertebrate cells causes centrosome detachment and results in HSET depletion at centrosomes, a phenotype also observed in CEP215-deficient patient-derived cells. Moreover, in cancer cells with centrosome amplification, the CEP215–HSET complex promotes the clustering of extra centrosomes into pseudo-bipolar spindles, thereby ensuring viable cell division. Therefore, stabilization of the centrosome–spindle pole interface by the CEP215–HSET complex could promote survival of cancer cells containing supernumerary centrosomes. PMID:26987684

  3. Clustering dynamics of the metal-benzene sandwich complex: the role of microscopic structure of the solute in the bis(eta6-benzene)chromium .Arn Clusters (n = 1-15).

    PubMed

    Choi, Kyo-Won; Choi, Sunyoung; Ahn, Doo-Sik; Han, Songhee; Kang, Tae Yeon; Baek, Sun Jong; Kim, Sang Kyu

    2008-08-07

    Ar clustering dynamics around the metal-benzene sandwich complex, bis(eta (6)-benzene)chromium: Cr(Bz) 2, is found to occur in two distinct regimes. The shift of the ionization potential (IP) upon the addition of Ar is measured to be 151 cm (-1), and it is constant until the number of Ar solvents ( n) becomes 6. The IP shift per Ar is found to be suddenly decreased to 82 cm (-1) for the clusters of n = 7-12. The cluster distribution indicates that the n = 6 cluster is most populated in the molecular beam. These experimental findings with the aid of ab initio calculation indicate that the first six Ar solvent molecules are attached to top and bottom of Cr(Bz) 2 to give the robust structure for the Cr(Bz) 2-Ar 6 cluster whereas the next six Ar molecules are gathered on the side of the solute core to give the highly symmetric structure of the Cr(Bz) 2-Ar 12 cluster.

  4. Scab resistance in 'Geneva' apple is conditioned by a resistance gene cluster with complex genetic control.

    PubMed

    Bastiaanse, Héloïse; Bassett, Heather C M; Kirk, Christopher; Gardiner, Susan E; Deng, Cecilia; Groenworld, Remmelt; Chagné, David; Bus, Vincent G M

    2016-02-01

    Apple scab, caused by the fungal pathogen Venturia inaequalis, is one of the most severe diseases of apple worldwide. It is the most studied plant-pathogen interaction involving a woody species using modern genetic, genomic, proteomic and bioinformatic approaches in both species. Although 'Geneva' apple was recognized long ago as a potential source of resistance to scab, this resistance has not been characterized previously. Differential interactions between various monoconidial isolates of V. inaequalis and six segregating F1 and F2 populations indicate the presence of at least five loci governing the resistance in 'Geneva'. The 17 chromosomes of apple were screened using genotyping-by-sequencing, as well as single marker mapping, to position loci controlling the V. inaequalis resistance on linkage group 4. Next, we fine mapped a 5-cM region containing five loci conferring both dominant and recessive scab resistance to the distal end of the linkage group. This region corresponds to 2.2 Mbp (from 20.3 to 22.5 Mbp) on the physical map of 'Golden Delicious' containing nine candidate nucleotide-binding site leucine-rich repeat (NBS-LRR) resistance genes. This study increases our understanding of the complex genetic basis of apple scab resistance conferred by 'Geneva', as well as the gene-for-gene (GfG) relationships between the effector genes in the pathogen and resistance genes in the host.

  5. Complex magnetic structure of clusters and chains of Ni and Fe on Pt(111)

    PubMed Central

    Bezerra-Neto, Manoel M.; Ribeiro, Marcelo S.; Sanyal, Biplab; Bergman, Anders; Muniz, Roberto B.; Eriksson, Olle; Klautau, Angela B.

    2013-01-01

    We present an approach to control the magnetic structure of adatoms adsorbed on a substrate having a high magnetic susceptibility. Using finite Ni-Pt and Fe-Pt nanowires and nanostructures on Pt(111) surfaces, our ab initio results show that it is possible to tune the exchange interaction and magnetic configuration of magnetic adatoms (Fe or Ni) by introducing different numbers of Pt atoms to link them, or by including edge effects. The exchange interaction between Ni (or Fe) adatoms on Pt(111) can be considerably increased by introducing Pt chains to link them. The magnetic ordering can be regulated allowing for ferromagnetic or antiferromagnetic configurations. Noncollinear magnetic alignments can also be stabilized by changing the number of Pt-mediated atoms. An Fe-Pt triangularly-shaped nanostructure adsorbed on Pt(111) shows the most complex magnetic structure of the systems considered here: a spin-spiral type of magnetic order that changes its propagation direction at the triangle vertices. PMID:24165828

  6. Three tetranuclear copper(II) cluster-based complexes constructed from 4-amino-1,2,4-triazole and different aromatic carboxylates: Assembly, structures, electrochemical and magnetic properties

    SciTech Connect

    Wang, Xiu-Li; Zhao, Wei; Zhang, Ju-Wen; Lu, Qi-Lin

    2013-02-15

    Three new tetranuclear copper(II) cluster-based complexes constructed from 4-amino-1,2,4-triazole (atrz) and three types of aromatic carboxylates, [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(DNBA){sub 6}] (1), [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(1,3-BDC){sub 3}]{center_dot}2H{sub 2}O (2) and [Cu{sub 4}({mu}{sub 3}-OH){sub 2}(atrz){sub 2}(SIP){sub 2}]{center_dot}4H{sub 2}O (3) (HDNBA=3,5-dinitrobenzoic acid, 1,3-H{sub 2}BDC=1,3-benzenedicarboxylic acid and NaH{sub 2}SIP=sodium 5-sulfoisophthalate), have been hydrothermally synthesized and structurally characterized. Complex 1 displays a single-molecular Cu{sup II}{sub 4} cluster structure, which is further connected by the intermolecular hydrogen-bonding interactions to form a 2D supramolecular layer. In 2, there also exist tetranuclear Cu{sup II}{sub 4} clusters, which are linked by the 1,3-BDC anions to give a 3D NaCl-type framework. In 3, the Cu{sup II}{sub 4} clusters are connected by the carboxyl and sulfo groups of SIP anions to generate 3D (4,8)-connected framework with a (4{sup 10}{center_dot}6{sup 14}{center_dot}8{sup 4})(4{sup 5}{center_dot}6){sub 2} topology. The atrz ligand conduces to the construction of tetranuclear copper(II) clusters and the carboxylates with different non-carboxyl substituent show important effects on the final structures of the title complexes. The electrochemical and magnetic properties of 1-3 have been investigated. - Graphical abstract: Three tetranuclear copper(II) cluster-based complexes based on different carboxylates have been synthesized under hydrothermal conditions. The carboxylate anions play a key role in the formation of three different structures. Highlights: Black-Right-Pointing-Pointer Three new tetranuclear copper(II) cluster-based complexes have been obtained. Black-Right-Pointing-Pointer The atrz conduces to the construction of tetranuclear copper(II) clusters. Black-Right-Pointing-Pointer Carboxylates show important effect on the structures of

  7. Synthesis, structural and magnetic characterisation of iron(II/III), cobalt(II) and copper(II) cluster complexes of the polytopic ligand: N-(2-pyridyl)-3-carboxypropanamide.

    PubMed

    Russell, Mark E; Hawes, Chris S; Ferguson, Alan; Polson, Matthew I J; Chilton, Nicholas F; Moubaraki, Boujemaa; Murray, Keith S; Kruger, Paul E

    2013-10-07

    Herein we describe the synthesis, structural and magnetic characterisation of three transition metal cluster complexes that feature the polytopic ligand N-(2-pyridyl)-3-carboxypropanamide (H2L): [Fe3(III)Fe2(II)(HL)6(O)(H2O)3][ClO4]5·3MeCN·4H2O, 1, [Co8(HL)8(O)(OH)4(MeOH)3(H2O)]-[ClO4]3·5MeOH·2H2O, 2, and [Cu6(L(ox))4(MeOH)(H2O)3]·MeOH, 3. Complex 1 is a mixed valence penta-nuclear iron cluster containing the archetypal {Fe3(III)O} triangular basic carboxylate cluster at its core, with two Fe(II) ions above and below the core coordinated to three bidentate pyridyl-amide groups. The structure of the octanuclear Co(II) complex, 2, is based upon a central Co4 square with the remaining four Co(II) centres at the 'wing-tips' of the complex. The cluster core is replete with bridging oxide, hydroxide and carboxylate groups. Cluster 3 contains an oxidised derivative of the ligand, L(ox), generated in situ through hydroxylation of an α-carbon atom. This hexanuclear cluster has a 'barrel-like' core and contains Cu(II) ions in both square planar and square-based pyramidal geometries. Bridging between Cu(II) centres is furnished by alkoxide and carboxylate groups. Magnetic studies on 1-3 reveals dominant antiferro-magnetic interactions for 1 and 2, leading to small non-zero spin ground states, while 3 shows ferro-magnetic exchange between the Cu(II) centres to give an S = 3 spin ground state.

  8. Detecting hidden spatial and spatio-temporal structures in glasses and complex physical systems by multiresolution network clustering.

    PubMed

    Ronhovde, P; Chakrabarty, S; Hu, D; Sahu, M; Sahu, K K; Kelton, K F; Mauro, N A; Nussinov, Z

    2011-09-01

    We elaborate on a general method that we recently introduced for characterizing the "natural" structures in complex physical systems via multi-scale network analysis. The method is based on "community detection" wherein interacting particles are partitioned into an "ideal gas" of optimally decoupled groups of particles. Specifically, we construct a set of network representations ("replicas") of the physical system based on interatomic potentials and apply a multiscale clustering ("multiresolution community detection") analysis using information-based correlations among the replicas. Replicas may i) be different representations of an identical static system, ii) embody dynamics by considering replicas to be time separated snapshots of the system (with a tunable time separation), or iii) encode general correlations when different replicas correspond to different representations of the entire history of the system as it evolves in space-time. Inputs for our method are the inter-particle potentials or experimentally measured two (or higher order) particle correlations. We apply our method to computer simulations of a binary Kob-Andersen Lennard-Jones system in a mixture ratio of A(80)B(20) , a ternary model system with components "A", "B", and "C" in ratios of A(88)B(7)C(5) (as in Al(88)Y(7)Fe(5) , and to atomic coordinates in a Zr(80)Pt(20) system as gleaned by reverse Monte Carlo analysis of experimentally determined structure factors. We identify the dominant structures (disjoint or overlapping) and general length scales by analyzing extrema of the information theory measures. We speculate on possible links between i) physical transitions or crossovers and ii) changes in structures found by this method as well as phase transitions associated with the computational complexity of the community detection problem. We also briefly consider continuum approaches and discuss rigidity and the shear penetration depth in amorphous systems; this latter length scale increases as

  9. Functional characterization of diverse ring-hydroxylating oxygenases and induction of complex aromatic catabolic gene clusters in Sphingobium sp. PNB

    PubMed Central

    Khara, Pratick; Roy, Madhumita; Chakraborty, Joydeep; Ghosal, Debajyoti; Dutta, Tapan K.

    2014-01-01

    Sphingobium sp. PNB, like other sphingomonads, has multiple ring-hydroxylating oxygenase (RHO) genes. Three different fosmid clones have been sequenced to identify the putative genes responsible for the degradation of various aromatics in this bacterial strain. Comparison of the map of the catabolic genes with that of different sphingomonads revealed a similar arrangement of gene clusters that harbors seven sets of RHO terminal components and a sole set of electron transport (ET) proteins. The presence of distinctly conserved amino acid residues in ferredoxin and in silico molecular docking analyses of ferredoxin with the well characterized terminal oxygenase components indicated the structural uniqueness of the ET component in sphingomonads. The predicted substrate specificities, derived from the phylogenetic relationship of each of the RHOs, were examined based on transformation of putative substrates and their structural homologs by the recombinant strains expressing each of the oxygenases and the sole set of available ET proteins. The RHO AhdA1bA2b was functionally characterized for the first time and was found to be capable of transforming ethylbenzene, propylbenzene, cumene, p-cymene and biphenyl, in addition to a number of polycyclic aromatic hydrocarbons. Overexpression of aromatic catabolic genes in strain PNB, revealed by real-time PCR analyses, is a way forward to understand the complex regulation of degradative genes in sphingomonads. PMID:24918041

  10. Deficiency of the iron-sulfur clusters of mitochondrial reduced nicotinamide-adenine dinucleotide-ubiquinone oxidoreductase (complex I) in an infant with congenital lactic acidosis.

    PubMed

    Moreadith, R W; Batshaw, M L; Ohnishi, T; Kerr, D; Knox, B; Jackson, D; Hruban, R; Olson, J; Reynafarje, B; Lehninger, A L

    1984-09-01

    We report the case of an infant with hypoglycemia, progressive lactic acidosis, an increased serum lactate/pyruvate ratio, and elevated plasma alanine, who had a moderate to profound decrease in the ability of mitochondria from four organs to oxidize pyruvate, malate plus glutamate, citrate, and other NAD+-linked respiratory substrates. The capacity to oxidize the flavin adenine dinucleotide-linked substrate, succinate, was normal. The most pronounced deficiency was in skeletal muscle, the least in kidney mitochondria. Enzymatic assays on isolated mitochondria ruled out defects in complexes II, III, and IV of the respiratory chain. Further studies showed that the defect was localized in the inner membrane mitochondrial NADH-ubiquinone oxidoreductase (complex I). When ferricyanide was used as an artificial electron acceptor, complex I activity was normal, indicating that electrons from NADH could reduce the flavin mononucleotide cofactor. However, electron paramagnetic resonance spectroscopy performed on liver submitochondrial particles showed an almost total loss of the iron-sulfur clusters characteristic of complex I, whereas normal signals were noted for other mitochondrial iron-sulfur clusters. This infant is presented as the first reported case of congenital lactic acidosis caused by a deficiency of the iron-sulfur clusters of complex I of the mitochondrial electron transport chain.

  11. The Yeast Iron Regulatory Proteins Grx3/4 and Fra2 Form Heterodimeric Complexes Containing a [2Fe-2S] Cluster with Cysteinyl and Histidyl Ligation†

    PubMed Central

    Li, Haoran; Mapolelo, Daphne T.; Dingra, Nin N.; Naik, Sunil G.; Lees, Nicolas S.; Hoffman, Brian M.; Riggs-Gelasco, Pamela J.; Huynh, Boi Hanh; Johnson, Michael K.; Outten, Caryn E.

    2009-01-01

    The transcription of iron uptake and storage genes in S. cerevisiae is primarily regulated by the transcription factor Aft1. Nucleocytoplasmic shuttling of Aft1 is dependent upon mitochondrial Fe-S cluster biosynthesis via a signaling pathway that includes the cytosolic monothiol glutaredoxins (Grx3 and Grx4) and the BolA homologue Fra2. However the interactions between these proteins and the iron-dependent mechanism by which they control Aft1 localization are unclear. To reconstitute and characterize components of this signaling pathway in vitro, we have overexpressed yeast Fra2 and Grx3/4 in E. coli. We have shown that co-expression of recombinant Fra2 with Grx3 or Grx4 allows purification of a stable [2Fe-2S]2+ cluster-containing Fra2-Grx3 or Fra2-Grx4 heterodimeric complex. Reconstitution of a [2Fe-2S] cluster on Grx3 or Grx4 without Fra2 produces a [2Fe-2S]-bridged homodimer. UV-visible absorption and CD, resonance Raman, EPR, ENDOR, Mössbauer, and EXAFS studies of [2Fe-2S] Grx3/4 homodimers and the [2Fe-2S] Fra2-Grx3/4 heterodimers indicate that inclusion of Fra2 in the Grx3/4 Fe-S complex causes a change in the cluster stability and coordination environment. Taken together, our analytical, spectroscopic, and mutagenesis data indicate that Grx3/4 and Fra2 form a Fe-S-bridged heterodimeric complex with Fe ligands provided by the active site cysteine of Grx3/4, glutathione, and a histidine residue. Overall, these results suggest that the ability of the Fra2-Grx3/4 complex to assemble a [2Fe-2S] cluster may act as a signal to control the iron regulon in response to cellular iron status in yeast. PMID:19715344

  12. Structural diversity of copper-CO2 complexes: infrared spectra and structures of [Cu(CO2)n]- clusters.

    PubMed

    Knurr, Benjamin J; Weber, J Mathias

    2014-11-06

    We  present infrared spectra of  [Cu(CO2)n](-) (n = 2-9) clusters in the wavenumber range 1600-2400 cm(-1). The CO stretching modes in this region encode the structural nature of the cluster core and are interpreted with the aid of density functional theory. We find a variety of core species in [Cu(CO2)n](-) clusters, but the dominant core structure is a [Cu(CO2)2](-) core where the two CO2 ligands are bound to the Cu atom in a bidentate fashion. We compare the results of [Cu(CO2)n](-) clusters to those of other [M(CO2)n](-) clusters (M = Au, Ag, Co, Ni) to establish trends of how the metal-CO2 interaction depends on the metal partner.

  13. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters

    NASA Astrophysics Data System (ADS)

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M 2(μ 2-NO)]; (c) threefold nitrosyl bridges, [M 3(μ 3-NO)]; (d) σ/π-dihaptonitrosyls or " side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M 2(μ 2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M 3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  14. A structure-based analysis of the vibrational spectra of nitrosyl ligands in transition-metal coordination complexes and clusters.

    PubMed

    De La Cruz, Carlos; Sheppard, Norman

    2011-01-01

    The vibrational spectra of nitrogen monoxide or nitric oxide (NO) bonded to one or to several transition-metal (M) atom(s) in coordination and cluster compounds are analyzed in relation to the various types of such structures identified by diffraction methods. These structures are classified in: (a) terminal (linear and bent) nitrosyls, [M(σ-NO)] or [M(NO)]; (b) twofold nitrosyl bridges, [M2(μ2-NO)]; (c) threefold nitrosyl bridges, [M3(μ3-NO)]; (d) σ/π-dihaptonitrosyls or "side-on" nitrosyls; and (e) isonitrosyls (oxygen-bonded nitrosyls). Typical ranges for the values of internuclear N-O and M-N bond-distances and M-N-O bond-angles for linear nitrosyls are: 1.14-1.20 Å/1.60-1.90 Å/180-160° and for bent nitrosyls are 1.16-1.22 Å/1.80-2.00 Å/140-110°. The [M2(μ2-NO)] bridges have been divided into those that contain one or several metal-metal bonds and those without a formal metal/metal bond (M⋯M). Typical ranges for the M-M, N-O, M-N bond distances and M-N-M bond angles for the normal twofold NO bridges are: 2.30-3.00 Å/1.18-1.22 Å/1.80-2.00 Å/90-70°, whereas for the analogous ranges of the long twofold NO bridges these are 3.10-3.40 Å/1.20-1.24 Å/1.90-2.10 Å/130-110°. In both situations the N-O vector is approximately at right angle to the M-M (or M⋯M) vector within the experimental error; i.e. the NO group is symmetrical bonded to the two metal atoms. In contrast the threefold NO bridges can be symmetrically or unsymmetrically bonded to an M3-plane of a cluster compound. Characteristic values for the N-O and M-N bond-distances of these NO bridges are: 1.24-1.28 Å/1.80-1.90 Å, respectively. As few dihaptonitrosyl and isonitrosyl complexes are known, the structural features of these are discussed on an individual basis. The very extensive vibrational spectroscopy literature considered gives emphasis to the data from linearly bonded NO ligands in stable closed-shell metal complexes; i.e. those which are consistent with the

  15. Complexes of DNA Bases and Watson-Crick Base Pairs Interaction with Neutral Silver Agn (n = 8, 10, 12) Clusters: A DFT and TDDFT Study.

    PubMed

    Srivastava, Ruby

    2017-03-21

    We study the binding of the neutral Agn (n = 8, 10, 12) to the DNA base- adenine (A), guanine (G) and Watson-Crick -adenine-thymine (AT), guanine-cytosine (GC) pairs. Geometries of complexes were optimized at the DFT level using the hybrid B3LYP functional. LANL2DZ effective core potential (ECP) was used for silver and 6-31+G(**) was used for all other atoms. NBO charges were analyzed using the Natural population analysis. The absorption properties of Agn-A,G/WC complexes were also studied using time-dependent density functional theory (TDDFT). The absorption spectra for these complexes show wavelength in the visible region. It was revealed that silver clusters interact more strongly with WC pairs than with isolated DNA complexes. Furthermore, it was found that the electronic charge transferred from silver to isolated DNA clusters are less than the electronic charge transferred from silver to the Agn-WC complexes. The vertical ionization potential, vertical electron affinity, hardness and electrophilicity index of Agn-DNA/WC complexes have also been discussed.

  16. Differentiation of the gene clusters encoding botulinum neurotoxin type A complexes in Clostridium botulinum type A, Ab, and A(B) strains.

    PubMed

    Franciosa, Giovanna; Floridi, Francesca; Maugliani, Antonella; Aureli, Paolo

    2004-12-01

    We describe a strategy to identify the clusters of genes encoding components of the botulinum toxin type A (boNT/A) complexes in 57 strains of Clostridium botulinum types A, Ab, and A(B) isolated in Italy and in the United States from different sources. Specifically, we combined the results of PCR for detecting the ha33 and/or p47 genes with those of boNT/A PCR-restriction fragment length polymorphism analysis. Three different type A toxin gene clusters were revealed; type A1 was predominant among the strains from the United States, whereas type A2 predominated among the Italian strains, suggesting a geographic distinction between strains. By contrast, no relationship between the toxin gene clusters and the clinical or food source of strains was evident. In two C. botulinum type A isolates from the United States, we recognized a third type A toxin gene cluster (designated type A3) which was similar to that previously described only for C. botulinum type A(B) and Ab strains. Total genomic DNA from the strains was subjected to pulsed-filed gel electrophoresis and randomly amplified polymorphic DNA analyses, and the results were consistent with the boNT/A gene clusters obtained.

  17. Differentiation of the Gene Clusters Encoding Botulinum Neurotoxin Type A Complexes in Clostridium botulinum Type A, Ab, and A(B) Strains

    PubMed Central

    Franciosa, Giovanna; Floridi, Francesca; Maugliani, Antonella; Aureli, Paolo

    2004-01-01

    We describe a strategy to identify the clusters of genes encoding components of the botulinum toxin type A (boNT/A) complexes in 57 strains of Clostridium botulinum types A, Ab, and A(B) isolated in Italy and in the United States from different sources. Specifically, we combined the results of PCR for detecting the ha33 and/or p47 genes with those of boNT/A PCR-restriction fragment length polymorphism analysis. Three different type A toxin gene clusters were revealed; type A1 was predominant among the strains from the United States, whereas type A2 predominated among the Italian strains, suggesting a geographic distinction between strains. By contrast, no relationship between the toxin gene clusters and the clinical or food source of strains was evident. In two C. botulinum type A isolates from the United States, we recognized a third type A toxin gene cluster (designated type A3) which was similar to that previously described only for C. botulinum type A(B) and Ab strains. Total genomic DNA from the strains was subjected to pulsed-filed gel electrophoresis and randomly amplified polymorphic DNA analyses, and the results were consistent with the boNT/A gene clusters obtained. PMID:15574917

  18. Path-integral molecular dynamics simulations of BeO embedded in helium clusters: Formation of the stable HeBeO complex

    NASA Astrophysics Data System (ADS)

    Motegi, Haruki; Kakizaki, Akira; Takayanagi, Toshiyuki; Taketsugu, Yuriko; Taketsugu, Tetsuya; Shiga, Motoyuki

    2008-12-01

    Path-integral molecular dynamics simulations have been performed to understand the quantum helium solvation structures in the He nBeO cluster up to n = 100. Our simulations show that one helium atom is strongly bound to BeO to form HeBeO and that the first solvation shell around the HeBeO complex includes roughly 12-14 helium atoms. The second solvation structure was also observed for n > 20. Both the first and second solvation shells show an anisotropic behavior but the anisotropy for the second solvation shell was found to be much weaker than that for the first solvation shell, as expected. The present simulations suggest that the HeBeO complex may be formed in large helium clusters.

  19. Friedreich's Ataxia Variants I154F and W155R Diminish Frataxin-Based Activation of the Iron-Sulfur Cluster Assembly Complex

    SciTech Connect

    Tsai, Chi-Lin; Bridwell-Rabb, Jennifer; Barondeau, David P

    2011-11-07

    Friedreich's ataxia (FRDA) is a progressive neurodegenerative disease that has been linked to defects in the protein frataxin (Fxn). Most FRDA patients have a GAA expansion in the first intron of their Fxn gene that decreases protein expression. Some FRDA patients have a GAA expansion on one allele and a missense mutation on the other allele. Few functional details are known for the ~15 different missense mutations identified in FRDA patients. Here in vitro evidence is presented that indicates the FRDA I154F and W155R variants bind more weakly to the complex of Nfs1, Isd11, and Isu2 and thereby are defective in forming the four-component SDUF complex that constitutes the core of the Fe-S cluster assembly machine. The binding affinities follow the trend Fxn ~ I154F > W155F > W155A ~ W155R. The Fxn variants also have diminished ability to function as part of the SDUF complex to stimulate the cysteine desulfurase reaction and facilitate Fe-S cluster assembly. Four crystal structures, including the first for a FRDA variant, reveal specific rearrangements associated with the loss of function and lead to a model for Fxn-based activation of the Fe-S cluster assembly complex. Importantly, the weaker binding and lower activity for FRDA variants correlate with the severity of disease progression. Together, these results suggest that Fxn facilitates sulfur transfer from Nfs1 to Isu2 and that these in vitro assays are sensitive and appropriate for deciphering functional defects and mechanistic details for human Fe-S cluster biosynthesis.

  20. Semiquinone and Cluster N6 Signals in His-tagged Proton-translocating NADH:Ubiquinone Oxidoreductase (Complex I) from Escherichia coli*

    PubMed Central

    Narayanan, Madhavan; Gabrieli, David J.; Leung, Steven A.; Elguindy, Mahmoud M.; Glaser, Carl A.; Saju, Nitha; Sinha, Subhash C.; Nakamaru-Ogiso, Eiko

    2013-01-01

    NADH:ubiquinone oxidoreductase (complex I) pumps protons across the membrane using downhill redox energy. The Escherichia coli complex I consists of 13 different subunits named NuoA-N coded by the nuo operon. Due to the low abundance of the protein and some difficulty with the genetic manipulation of its large ∼15-kb operon, purification of E. coli complex I has been technically challenging. Here, we generated a new strain in which a polyhistidine sequence was inserted upstream of nuoE in the operon. This allowed us to prepare large amounts of highly pure and active complex I by efficient affinity purification. The purified complex I contained 0.94 ± 0.1 mol of FMN, 29.0 ± 0.37 mol of iron, and 1.99 ± 0.07 mol of ubiquinone/1 mol of complex I. The extinction coefficient of isolated complex I was 495 mm−1 cm−1 at 274 nm and 50.3 mm−1 cm−1 at 410 nm. NADH:ferricyanide activity was 219 ± 9.7 μmol/min/mg by using HEPES-Bis-Tris propane, pH 7.5. Detailed EPR analyses revealed two additional iron-sulfur cluster signals, N6a and N6b, in addition to previously assigned signals. Furthermore, we found small but significant semiquinone signal(s), which have been reported only for bovine complex I. The line width was ∼12 G, indicating its neutral semiquinone form. More than 90% of the semiquinone signal originated from the single entity with P½ (half-saturation power level) = 1.85 milliwatts. The semiquinone signal(s) decreased by 60% when with asimicin, a potent complex I inhibitor. The functional role of semiquinone and the EPR assignment of clusters N6a/N6b are discussed. PMID:23543743

  1. Crystal structure of yeast monothiol glutaredoxin Grx6 in complex with a glutathione-coordinated [2Fe–2S] cluster

    PubMed Central

    Abdalla, Mohnad; Dai, Ya-Nan; Chi, Chang-Biao; Cheng, Wang; Cao, Dong-Dong; Zhou, Kang; Ali, Wafa; Chen, Yuxing; Zhou, Cong-Zhao

    2016-01-01

    Glutaredoxins (Grxs) constitute a superfamily of proteins that perform diverse biological functions. The Saccharomyces cerevisiae glutaredoxin Grx6 not only serves as a glutathione (GSH)-dependent oxidoreductase and as a GSH transferase, but also as an essential [2Fe–2S]-binding protein. Here, the dimeric structure of the C-terminal domain of Grx6 (holo Grx6C), bridged by one [2Fe–2S] cluster coordinated by the active-site Cys136 and two external GSH molecules, is reported. Structural comparison combined with multiple-sequence alignment demonstrated that holo Grx6C is similar to the [2Fe–2S] cluster-incorporated dithiol Grxs, which share a highly conserved [2Fe–2S] cluster-binding pattern and dimeric conformation that is distinct from the previously identified [2Fe–2S] cluster-ligated monothiol Grxs. PMID:27710937

  2. Altered structure of the Mn4Ca cluster in the oxygen-evolving complex of photosystem II by a histidine ligand mutation.

    PubMed

    Yano, Junko; Walker, Lee M; Strickler, Melodie A; Service, Rachel J; Yachandra, Vittal K; Debus, Richard J

    2011-03-18

    The effect of replacing a histidine ligand on the properties of the oxygen-evolving complex (OEC) and the structure of the Mn(4)Ca cluster in Photosystem II (PSII) is studied by x-ray absorption spectroscopy using PSII core complexes from the Synechocystis sp. PCC 6803 D1 polypeptide mutant H332E. In the x-ray crystallographic structures of PSII, D1-His(332) has been assigned as a direct ligand of a manganese ion, and the mutation of this histidine ligand to glutamate has been reported to prevent the advancement of the OEC beyond the S(2)Yz(•) intermediate state. The manganese K-edge (1s core electron to 4p) absorption spectrum of D1-H332E shifts to a lower energy compared with that of the native WT samples, suggesting that the electronic structure of the manganese cluster is affected by the presence of the additional negative charge on the OEC of the mutant. The extended x-ray absorption spectrum shows that the geometric structure of the cluster is altered substantially from that of the native WT state, resulting in an elongation of manganese-ligand and manganese-manganese interactions in the mutant. The strontium-H332E mutant, in which calcium is substituted by strontium, confirms that strontium (calcium) is a part of the altered cluster. The structural perturbations caused by the D1-H332E mutation are much larger than those produced by any biochemical treatment or mutation examined previously with x-ray absorption spectroscopy. The substantial structural changes provide an explanation not only for the altered properties of the D1-H332E mutant but also the importance of the histidine ligand for proper assembly of the Mn(4)Ca cluster.

  3. Density-based clustering: A ‘landscape view’ of multi-channel neural data for inference and dynamic complexity analysis

    PubMed Central

    Gigante, Guido; Del Giudice, Paolo

    2017-01-01

    Two, partially interwoven, hot topics in the analysis and statistical modeling of neural data, are the development of efficient and informative representations of the time series derived from multiple neural recordings, and the extraction of information about the connectivity structure of the underlying neural network from the recorded neural activities. In the present paper we show that state-space clustering can provide an easy and effective option for reducing the dimensionality of multiple neural time series, that it can improve inference of synaptic couplings from neural activities, and that it can also allow the construction of a compact representation of the multi-dimensional dynamics, that easily lends itself to complexity measures. We apply a variant of the ‘mean-shift’ algorithm to perform state-space clustering, and validate it on an Hopfield network in the glassy phase, in which metastable states are largely uncorrelated from memories embedded in the synaptic matrix. In this context, we show that the neural states identified as clusters’ centroids offer a parsimonious parametrization of the synaptic matrix, which allows a significant improvement in inferring the synaptic couplings from the neural activities. Moving to the more realistic case of a multi-modular spiking network, with spike-frequency adaptation inducing history-dependent effects, we propose a procedure inspired by Boltzmann learning, but extending its domain of application, to learn inter-module synaptic couplings so that the spiking network reproduces a prescribed pattern of spatial correlations; we then illustrate, in the spiking network, how clustering is effective in extracting relevant features of the network’s state-space landscape. Finally, we show that the knowledge of the cluster structure allows casting the multi-dimensional neural dynamics in the form of a symbolic dynamics of transitions between clusters; as an illustration of the potential of such reduction, we define

  4. HIGH-RESOLUTION STUDY OF THE CLUSTER COMPLEXES IN A LENSED SPIRAL AT REDSHIFT 1.5: CONSTRAINTS ON THE BULGE FORMATION AND DISK EVOLUTION

    SciTech Connect

    Adamo, Angela; Oestlin, G.; Zackrisson, E.; Guaita, L.; Bastian, N.; Livermore, R. C.

    2013-04-01

    We analyze the clump population of the spiral galaxy Sp 1149 at redshift 1.5. Located behind the galaxy cluster MACS J1149.5+2223, Sp 1149 has been significantly magnified allowing us to study the galaxy on physical scales down to {approx}100 pc. The galaxy cluster frame is among the targets of the Cluster Lensing And Supernova survey with Hubble (CLASH), an ongoing Hubble Space Telescope (HST) Multi-Cycle Treasury program. We have used the publicly available multi-band imaging data set to reconstruct the spectral energy distributions of the clumps in Sp 1149, and derive, by means of stellar evolutionary models, their physical properties. We found that 40% of the clumps observed in Sp 1149 are older than 30 Myr and can be as old as 300 Myr. These are also the more massive (luminous) clumps in the galaxy. Among the complexes in the local reference sample, the star-forming knots in luminous blue compact galaxies could be considered progenitor analogs of these long-lived clumps. The remaining 60% of clumps have colors comparable to local cluster complexes, suggesting a similar young age. We observe that the Sp 1149 clumps follow the M{proportional_to}R {sup 2} relation similar to local cluster complexes, suggesting similar formation mechanisms although they may have different initial conditions (e.g., higher gas surface densities). We suggest that the galaxy is experiencing a slow decline in star formation rate and a likely transitional phase toward a more quiescent star formation mode. The older clumps have survived between 6 and 20 dynamical times and are all located at projected distances smaller than 4 kpc from the center. Their current location suggests migration toward the center and the possibility of being the building blocks of the bulge. On the other hand, the dynamical timescale of the younger clumps is significantly shorter, meaning that they are quite close to their birthplace. We show that the clumps of Sp 1149 may account for the expected metal

  5. High-resolution Study of the Cluster Complexes in a Lensed Spiral at Redshift 1.5: Constraints on the Bulge Formation and Disk Evolution

    NASA Astrophysics Data System (ADS)

    Adamo, Angela; Östlin, G.; Bastian, N.; Zackrisson, E.; Livermore, R. C.; Guaita, L.

    2013-04-01

    We analyze the clump population of the spiral galaxy Sp 1149 at redshift 1.5. Located behind the galaxy cluster MACS J1149.5+2223, Sp 1149 has been significantly magnified allowing us to study the galaxy on physical scales down to ~100 pc. The galaxy cluster frame is among the targets of the Cluster Lensing And Supernova survey with Hubble (CLASH), an ongoing Hubble Space Telescope (HST) Multi-Cycle Treasury program. We have used the publicly available multi-band imaging data set to reconstruct the spectral energy distributions of the clumps in Sp 1149, and derive, by means of stellar evolutionary models, their physical properties. We found that 40% of the clumps observed in Sp 1149 are older than 30 Myr and can be as old as 300 Myr. These are also the more massive (luminous) clumps in the galaxy. Among the complexes in the local reference sample, the star-forming knots in luminous blue compact galaxies could be considered progenitor analogs of these long-lived clumps. The remaining 60% of clumps have colors comparable to local cluster complexes, suggesting a similar young age. We observe that the Sp 1149 clumps follow the MvpropR 2 relation similar to local cluster complexes, suggesting similar formation mechanisms although they may have different initial conditions (e.g., higher gas surface densities). We suggest that the galaxy is experiencing a slow decline in star formation rate and a likely transitional phase toward a more quiescent star formation mode. The older clumps have survived between 6 and 20 dynamical times and are all located at projected distances smaller than 4 kpc from the center. Their current location suggests migration toward the center and the possibility of being the building blocks of the bulge. On the other hand, the dynamical timescale of the younger clumps is significantly shorter, meaning that they are quite close to their birthplace. We show that the clumps of Sp 1149 may account for the expected metal-rich globular cluster population

  6. Protons bound to the Mn cluster in photosystem II oxygen evolving complex detected by proton matrix ENDOR.

    PubMed

    Yamada, Hiroiku; Mino, Hiroyuki; Itoh, Shigeru

    2007-03-01

    Protons in the vicinity of the oxygen-evolving manganese cluster in photosystem II were studied by proton matrix ENDOR. Six pairs of proton ENDOR signals were detected in both the S(0) and S(2) states of the Mn-cluster. Two pairs of signals that show hyperfine constants of 2.3/2.2 and 4.0 MHz, respectively, disappeared after D(2)O incubation in both states. The signals with 2.3/2.2 MHz hyperfine constants in S(0) and S(2) state multiline disappeared after 3 h of D(2)O incubation in the S(0) and S(1) states, respectively. The signal with 4.0 MHz hyperfine constants in S(0) state multiline disappeared after 3 h of D(2)O incubation in the S(0) state, while the similar signal in S(2) state multiline disappeared only after 24 h of D(2)O incubation in the S(1) state. The different proton exchange rates seem to be ascribable to the change in affinities of water molecules to the variation in oxidation state of the Mn cluster during the water oxidation cycle. Based on the point dipole approximation, the distances between the center of electronic spin of the Mn cluster and the exchangeable protons were estimated to be 3.3/3.2 and 2.7 A, respectively. These short distances suggest the protons belong to the water molecules ligated to the manganese cluster. We propose a model for the binding of water to the manganese cluster based on these results.

  7. A possible evolutionary origin for the Mn4 cluster of the photosynthetic water oxidation complex from natural MnO2 precipitates in the early ocean.

    PubMed

    Sauer, Kenneth; Yachandra, Vittal K

    2002-06-25

    The photosynthetic water oxidation complex consists of a cluster of four Mn atoms bridged by O atoms, associated with Ca2+ and Cl-, and incorporated into protein. The structure is similar in higher plants and algae, as well as in cyanobacteria of more ancient lineage, dating back more than 2.5 billion years ago on Earth. It has been proposed that the proto-enzyme derived from a component of a natural early marine manganese precipitate that contained a CaMn4O9 cluster. A variety of MnO2 minerals are found in nature. Three major classes are spinels, sheet-like layered structures, and three-dimensional networks that contain parallel tunnels. These relatively open structures readily incorporate cations (Na+, Li+, Mg2+, Ca2+, Ba2+, H+, and even Mn2+) and water. The minerals have different ratios of Mn(III) and Mn(IV) octahedrally coordinated to oxygens. Using x-ray spectroscopy we compare the chemical structures of Mn in the minerals with what is known about the arrangement in the water oxidation complex to define the parameters of a structural model for the photosynthetic catalytic site. This comparison provides for the structural model a set of candidate Mn(4) clusters-some previously proposed and considered and others entirely novel.

  8. A possible evolutionary origin for the Mn4 cluster of the photosynthetic water oxidation complex from natural MnO2 precipitates in the early ocean

    SciTech Connect

    Sauer, Kenneth; Yachandra, Vittal K.

    2002-04-30

    The photosynthetic water oxidation complex consists of a cluster of 4 Mn atoms bridged by O atoms, associated with Ca2+ and Cl- and incorporated into protein. The structure is similar in higher plants and algae, as well as in cyanobacteria of more ancient lineage, dating back more than 2.5 Ga on Earth. It has been proposed that the proto-enzyme derived from a component of a natural early marine manganese precipitate that contained a CaMn4O9 cluster. A variety of MnO2 minerals is found in nature. Three major classes are spinels, sheet-like layered structures and 3-dimensional networks that contain parallel tunnels. These relatively open structures readily incorporate cations (Na+, Li+, Mg2+, Ca2+, Ba2+, H+ and even Mn2+) and water. The minerals have different ratios of Mn(III) and Mn(IV) octahedrally coordinated to oxygens. Using X-ray spectroscopy we compare the chemical structures of Mn in the minerals with what is known about the arrangement in the water-oxidation complex to define the parameters of a structural model for the photosynthetic catalytic site. This comparison provides for the structural model a set of candidate Mn4 clusters -- some previously proposed and considered and others entirely novel.

  9. Mixed-metal chloro sulfido cluster complex of molybdenum and platinum, (Mo sub 3 Pt sub 2 S sub 4 Cl sub 4 (PEt sub 3 ) sub 6 )

    SciTech Connect

    Saito, Taro; Tsuboi, Toshio; Kajitani, Yoshimichi; Yamagata, Tsuneaki; Imoto, Hideo )

    1991-09-04

    In the authors recent publication, syntheses of mixed-metal chloro sulfido and chloro selenido complexes of molybdenum and nickel were reported. They were prepared by the reaction of (Mo{sub 3}X{sub 4}Cl{sub 4}(PEt{sub 3}){sub 3}(MeOH){sub 2}) (X = S, Se){sup 2} with Ni(cod){sub 2} (cod = 1,5-cyclooctadiene). In the present study, another excellent building block compound, Pt(cot){sub 2}, was reacted with the same trinuclear molybdenum complex, and the mixed-metal cluster complex (Mo{sub 3}Pt{sub 2}S{sub 4}Cl{sub 4}(PEt{sub 3}){sub 6}) (1) with an unexpected structure was obtained.

  10. Extensive Variation in the O-Antigen Gene Cluster within One Salmonella enterica Serogroup Reveals an Unexpected Complex History

    PubMed Central

    Wang, Lei; Andrianopoulos, Kanella; Liu, Dan; Popoff, Michel Y.; Reeves, Peter R.

    2002-01-01

    The 46 serogroups of Salmonella enterica have different O-antigens, and each is thought to have a specific form of the O-antigen cluster. Comparison of the 145 serovars of serogroup B revealed much more intraserogroup genetic diversity than expected. The O27 factor, due to an α 1-6 linkage between O units in place of the more common α 1-2 linkage and previously thought to be due to a converting bacteriophage, is now shown to be due to a wzyα(1-6) gene located within the major gene cluster. Surprisingly a remnant of this gene in all O27− serovars shows that the ancestor was O27+. There are six distinct gene cluster forms, five apparently derived by a series of deletions and one by an insertion from an ancestral O27+ form present in 57 serovars. The history of the gene cluster and movement between subspecies I and II can be traced. Two of the derivative forms still have a functional wzyα(1-6) gene, while in three it has been inactivated by deletion or insertion. Two of the forms lacking a functional wzyα(1-6) gene have the wzyα(1-2) gene first described for strain LT2 as rfc, whereas for the third the wzy gene has not been located. PMID:11872718

  11. Complex-to-Predict Generational Shift between Nested and Clustered Organization of Individual Prey Networks in Digger Wasps

    PubMed Central

    Ballesteros, Yolanda; Polidori, Carlo; Tormos, José; Baños-Picón, Laura; Asís, Josep Daniel

    2014-01-01

    Although diet has traditionally been considered to be a property of the species or populations as a whole, there is nowadays extensive knowledge that individual specialization is widespread among animal populations. Nevertheless, the factors determining the shape of interactions within food webs remain largely undiscovered, especially in predatory insects. We used an aggregation of the digger wasp Bembix merceti to 1) analyse patterns of individual prey use across three flying seasons in a network–based context; and 2) test the effect of four potential factors that might explain network topologies (wasp mass, nest spatial distribution, simultaneous nest-provisioning, prey availability). Inter-individual diet variation was found in all three years, under different predator-prey network topologies: Individuals arranged in dietary clusters and displayed a checkerboard pattern in 2009, but showed nestedness in 2008 and 2010. Network topologies were not fully explained by the tested factors. Larger females consumed a higher proportion of the total number of prey species captured by the population as a whole, in such a way that nested patterns may arise from mass-dependent prey spectrum width. Conversely, individuals with similar body mass didn’t form clusters. Nested patterns seemed to be associated with a greater availability of the main prey species (a proxy for reduced intra-specific competition). Thus, according with theory, clusters seemed to appear when competition increased. On the other hand, the nests of the individuals belonging to a given cluster were not more closely located, and neither did individuals within a cluster provision their nests simultaneously. Thus, a female-female copying behaviour during foraging was unlikely. In conclusion, wasp populations can maintain a considerable individual variation across years under different food web organizations. The tested factors only partially accounted for the shift in network properties, and new analyses

  12. Bacillus cereus Fnr binds a [4Fe-4S] cluster and forms a ternary complex with ResD and PlcR

    PubMed Central

    2012-01-01

    Background Bacillus cereus is a facultative anaerobe that causes diarrheal disease in humans. Diarrheal syndrome may result from the secretion of various virulence factors including hemolysin BL and nonhemolytic enterotoxin Nhe. Expression of genes encoding Hbl and Nhe is regulated by the two redox systems, ResDE and Fnr, and the virulence regulator PlcR. B. cereus Fnr is a member of the Crp/Fnr family of iron-sulfur (Fe-S) proteins. Only its apo-form has so far been studied. A major goal in deciphering the Fnr-dependent regulation of enterotoxin genes is thus to obtain and characterize holoFnr. Results Fnr has been subjected to in vitro Fe-S cluster reconstitution under anoxic conditions. UV-visible and EPR spectroscopic analyses together with the chemical estimation of the iron content indicated that Fnr binds one [4Fe-4S]2+ cluster per monomer. Atmospheric O2 causes disassembly of the Fe-S cluster, which exhibited a half-life of 15 min in air. Holo- and apoFnr have similar affinities for the nhe and hbl promoter regions, while holoFnr has a higher affinity for fnr promoter region than apoFnr. Both the apo- and holo-form of Fnr interact with ResD and PlcR to form a ternary complex. Conclusions Overall, this work shows that incorporation of the [4Fe-4S]2+ cluster is not required for DNA binding of Fnr to promoter regions of hbl and nhe enterotoxin genes or for the formation of a ternary complex with ResD and PlcR. This points to some new unusual properties of Fnr that may have physiological relevance in the redox regulation of enterotoxin gene regulation. PMID:22731107

  13. Malfunctioning of the Iron–Sulfur Cluster Assembly Machinery in Saccharomyces cerevisiae Produces Oxidative Stress via an Iron-Dependent Mechanism, Causing Dysfunction in Respiratory Complexes

    PubMed Central

    Gomez, Mauricio; Pérez-Gallardo, Rocío V.; Sánchez, Luis A.; Díaz-Pérez, Alma L.; Cortés-Rojo, Christian; Meza Carmen, Victor; Saavedra-Molina, Alfredo; Lara-Romero, Javier; Jiménez-Sandoval, Sergio; Rodríguez, Francisco; Rodríguez-Zavala, José S.; Campos-García, Jesús

    2014-01-01

    Biogenesis and recycling of iron–sulfur (Fe–S) clusters play important roles in the iron homeostasis mechanisms involved in mitochondrial function. In Saccharomyces cerevisiae, the Fe–S clusters are assembled into apoproteins by the iron–sulfur cluster machinery (ISC). The aim of the present study was to determine the effects of ISC gene deletion and consequent iron release under oxidative stress conditions on mitochondrial functionality in S. cerevisiae. Reactive oxygen species (ROS) generation, caused by H2O2, menadione, or ethanol, was associated with a loss of iron homeostasis and exacerbated by ISC system dysfunction. ISC mutants showed increased free Fe2+ content, exacerbated by ROS-inducers, causing an increase in ROS, which was decreased by the addition of an iron chelator. Our study suggests that the increment in free Fe2+ associated with ROS generation may have originated from mitochondria, probably Fe–S cluster proteins, under both normal and oxidative stress conditions, suggesting that Fe–S cluster anabolism is affected. Raman spectroscopy analysis and immunoblotting indicated that in mitochondria from SSQ1 and ISA1 mutants, the content of [Fe–S] centers was decreased, as was formation of Rieske protein-dependent supercomplex III2IV2, but this was not observed in the iron-deficient ATX1 and MRS4 mutants. In addition, the activity of complexes II and IV from the electron transport chain (ETC) was impaired or totally abolished in SSQ1 and ISA1 mutants. These results confirm that the ISC system plays important roles in iron homeostasis, ROS stress, and in assembly of supercomplexes III2IV2 and III2IV1, thus affecting the functionality of the respiratory chain. PMID:25356756

  14. Size evolution relativistic DFT-QTAIM study on the gold cluster complexes Au4-S-CnH2n-S‧-Au4‧ (n = 2-5)

    NASA Astrophysics Data System (ADS)

    Rodríguez, Juan I.; Uribe, Emilbus A.; Baltazar-Méndez, María I.; Autschbach, Jochen; Castillo-Alvarado, F. L.; Gutiérrez-González, Israel

    2016-09-01

    We introduce relativistic density functional theory (DFT) calculations on the gold cluster complexes (cluster-molecule-cluster) Au4-S-CnH2n-S‧-Au4‧ (n = 2-5). The structural, electronic and relativistic (ZORA) Bader's quantum theory of atoms in molecules (QTAIM) properties of the two lowest-energy complex isomers were computed as a function of the alkanedithiol size (n). The lowest-energy isomer is a triplet spin state independently of the complex size. According to QTAIM, the Au-Au and S-Au bonds are classified as closed shell (non-covalent) type. The HOMO-LUMO gap of the cluster complexes shows a zigzag behavior typical of gold nanoclusters with respect to the size of the alkanedithiol chain (n).

  15. Interaction between Nbp35 and Cfd1 Proteins of Cytosolic Fe-S Cluster Assembly Reveals a Stable Complex Formation in Entamoeba histolytica

    PubMed Central

    Anwar, Shadab; Dikhit, Manas Ranjan; Singh, Krishn Pratap; Kar, Rajiv Kumar; Zaidi, Amir; Sahoo, Ganesh Chandra; Roy, Awadh Kishore; Nozaki, Tomoyoshi; Das, Pradeep; Ali, Vahab

    2014-01-01

    Iron-Sulfur (Fe-S) proteins are involved in many biological functions such as electron transport, photosynthesis, regulation of gene expression and enzymatic activities. Biosynthesis and transfer of Fe-S clusters depend on Fe-S clusters assembly processes such as ISC, SUF, NIF, and CIA systems. Unlike other eukaryotes which possess ISC and CIA systems, amitochondriate Entamoeba histolytica has retained NIF & CIA systems for Fe-S cluster assembly in the cytosol. In the present study, we have elucidated interaction between two proteins of E. histolytica CIA system, Cytosolic Fe-S cluster deficient 1 (Cfd1) protein and Nucleotide binding protein 35 (Nbp35). In-silico analysis showed that structural regions ranging from amino acid residues (P33-K35, G131-V135 and I147-E151) of Nbp35 and (G5-V6, M34-D39 and G46-A52) of Cfd1 are involved in the formation of protein-protein complex. Furthermore, Molecular dynamic (MD) simulations study suggested that hydrophobic forces surpass over hydrophilic forces between Nbp35 and Cfd1 and Van-der-Waal interaction plays crucial role in the formation of stable complex. Both proteins were separately cloned, expressed as recombinant fusion proteins in E. coli and purified to homogeneity by affinity column chromatography. Physical interaction between Nbp35 and Cfd1 proteins was confirmed in vitro by co-purification of recombinant Nbp35 with thrombin digested Cfd1 and in vivo by pull down assay and immunoprecipitation. The insilico, in vitro as well as in vivo results prove a stable interaction between these two proteins, supporting the possibility of its involvement in Fe-S cluster transfer to target apo-proteins through CIA machinery in E. histolytica. Our study indicates that initial synthesis of a Fe-S precursor in mitochondria is not necessary for the formation of Cfd1-Nbp35 complex. Thus, Cfd1 and Nbp35 with the help of cytosolic NifS and NifU proteins can participate in the maturation of non-mitosomal Fe-S proteins without any

  16. Cu(II)-azide polynuclear complexes of Cu4 building clusters with Schiff-base co-ligands: synthesis, structures, magnetic behavior and DFT studies.

    PubMed

    Mukherjee, Sandip; Mukherjee, Partha Sarathi

    2013-03-21

    Three new copper-azido complexes [Cu(4)(N(3))(8)(L(1))(2)](n) (1), [Cu(4)(N(3))(6)(L(2))(2)(H(2)O)(2)] (2), and [Cu(4)(N(3))(6)(L(3))(2)](n) (3) [L(1) is the imine resulting from the condensation of pyridine-2-carboxaldehyde with N-methylethylenediamine, HL(2) and HL(3) are the condensation products of 2-hydroxy-3-methoxybenzaldehyde with N,N-diethylethylenediamine and N-ethylethylenediamine respectively] have been synthesized by using 0.5 molar equivalents of the Schiff base ligands with Cu(NO(3))(2)·3H(2)O and an excess of NaN(3). Single crystal X-ray structures show that the basic unit of these complexes contains very similar Cu(II)(4) building blocks. While 1 and 3 have overall 1D structures, 2 forms discrete tetranuclear clusters due to blocking of two coordination sites on the tetranuclear cluster by water molecules. Magnetic susceptibility measurements over a wide range of temperatures exhibit the presence of both antiferromagnetic and ferromagnetic exchanges within the tetranuclear unit structures. Density functional theory calculations (using B3LYP functional and two different basis sets) have been performed on the complexes 1-3 to provide a qualitative theoretical interpretation of their overall magnetic behavior.

  17. Crystal Structure of Human Arginase l Complexed with Thiosemicarbazide Reveals an Unusual Thiocarbonly u-Sulfide Ligand in the Binuclear Manganese Cluster

    SciTech Connect

    Di Costanzo,L.; Pique, M.; Christianson, D.

    2007-01-01

    The crystal structure of the human arginase I-thiosemicarbazide complex reveals an unusual thiocarbonyl {mu}-sulfide ligand in the binuclear manganese cluster. The CS moiety of thiosemicarbazide bridges Mn2+A and Mn2+B with coordination distances of 2.6 and 2.4 Angstroms, respectively. Otherwise, the binding of thiosemicarbazide to human arginase I does not cause any significant structural changes in the active site. The crystal structure of the unliganded enzyme reveals a hydrogen-bonded water molecule that could support proton transfer between a {mu}-water molecule and H141 to regenerate the nucleophilic {mu}-hydroxide ion in the final step of catalysis.

  18. A CHANDRA STUDY OF THE ROSETTE STAR-FORMING COMPLEX. II. CLUSTERS IN THE ROSETTE MOLECULAR CLOUD

    SciTech Connect

    Wang Junfeng; Feigelson, Eric D.; Townsley, Leisa K.; Garmire, Gordon; Roman-Zuniga, Carlos G.; Lada, Elizabeth E-mail: edf@astro.psu.edu

    2009-05-01

    We explore here the young stellar populations in the Rosette Molecular Cloud (RMC) region with high spatial resolution X-ray images from the Chandra X-ray Observatory, which are effective in locating weak-lined T Tauri stars as well as disk-bearing young stars. A total of 395 X-ray point sources are detected, 299 of which (76%) have an optical or near-infrared (NIR) counterpart identified from deep FLAMINGOS images. From X-ray and mass sensitivity limits, we infer a total population of {approx}1700 young stars in the survey region. Based on smoothed stellar surface density maps, we investigate the spatial distribution of the X-ray sources and define three distinctive structures and substructures within them. Structures B and C are associated with previously known embedded IR clusters, while structure A is a new X-ray-identified unobscured cluster. A high-mass protostar RMCX no. 89 = IRAS 06306+0437 and its associated sparse cluster are studied. The different subregions are not coeval but do not show a simple spatial-age pattern. Disk fractions vary between subregions and are generally {approx}<20% of the total stellar population inferred from the X-ray survey. The data are consistent with speculations that triggered star formation around the H II region is present in the RMC, but do not support a simple sequential triggering process through the cloud interior. While a significant fraction of young stars are located in a distributed population throughout the RMC region, it is not clear if they originated in clustered environments.

  19. A Chandra Study of the Rosette Star-Forming Complex. II. Clusters in the Rosette Molecular Cloud

    NASA Astrophysics Data System (ADS)

    Wang, Junfeng; Feigelson, Eric D.; Townsley, Leisa K.; Román-Zúñiga, Carlos G.; Lada, Elizabeth; Garmire, Gordon

    2009-05-01

    We explore here the young stellar populations in the Rosette Molecular Cloud (RMC) region with high spatial resolution X-ray images from the Chandra X-ray Observatory, which are effective in locating weak-lined T Tauri stars as well as disk-bearing young stars. A total of 395 X-ray point sources are detected, 299 of which (76%) have an optical or near-infrared (NIR) counterpart identified from deep FLAMINGOS images. From X-ray and mass sensitivity limits, we infer a total population of ~1700 young stars in the survey region. Based on smoothed stellar surface density maps, we investigate the spatial distribution of the X-ray sources and define three distinctive structures and substructures within them. Structures B and C are associated with previously known embedded IR clusters, while structure A is a new X-ray-identified unobscured cluster. A high-mass protostar RMCX #89 = IRAS 06306+0437 and its associated sparse cluster are studied. The different subregions are not coeval but do not show a simple spatial-age pattern. Disk fractions vary between subregions and are generally lsim20% of the total stellar population inferred from the X-ray survey. The data are consistent with speculations that triggered star formation around the H II region is present in the RMC, but do not support a simple sequential triggering process through the cloud interior. While a significant fraction of young stars are located in a distributed population throughout the RMC region, it is not clear if they originated in clustered environments.

  20. Complexity.

    PubMed

    Gómez-Hernández, J Jaime

    2006-01-01

    It is difficult to define complexity in modeling. Complexity is often associated with uncertainty since modeling uncertainty is an intrinsically difficult task. However, modeling uncertainty does not require, necessarily, complex models, in the sense of a model requiring an unmanageable number of degrees of freedom to characterize the aquifer. The relationship between complexity, uncertainty, heterogeneity, and stochastic modeling is not simple. Aquifer models should be able to quantify the uncertainty of their predictions, which can be done using stochastic models that produce heterogeneous realizations of aquifer parameters. This is the type of complexity addressed in this article.

  1. Bismuth(III) complexes derived from α-amino acids: the impact of hydrolysis and oxido-cluster formation on their activity against Helicobacter pylori.

    PubMed

    Busse, Madleen; Border, Emily; Junk, Peter C; Ferrero, Richard L; Andrews, Philip C

    2014-12-28

    Eight bismuth(III) complexes derived from a variety of α-amino acids covering a range of physico-chemical properties (L-phenylalanine (Phe), L-proline (Pro), L-methionine (Met), L-cysteine (Cys), D,L-serine (Ser), L-tyrosine (Tyr), l-aspartic acid (Asp) and L-glutamic acid (Glu)) have been synthesised, characterised, and evaluated for their activity against Helicobacter pylori. The optimal synthetic procedure utilises [Bi(O(t)Bu)3], giving the complexes [BiL3] (L = Phe 1, Pro 2, Met 3, Ser 5, Tyr 6) and [Bi2L3] (L = Cys 4, Asp 7, Glu 8) cleanly and in good yield. However, the synthesis is sensitive to both temperature and moisture. The solubility and stability of the bismuth(III) complexes was investigated using ESI-MS. Almost all compounds (except for [Bi(Phe)3] and [Bi(Pro)3]) were found to be partially or completely soluble in aqueous solution giving a pH 2.5-5.0, indicating the presence of free α-amino acid and hydrolysis of the bismuth(III) complexes to polynuclear bismuth oxido-clusters. The results of the bactericidal studies against Helicobacter pylori demonstrate that this hydrolysis process impacts significantly on the observed Minimum Inhibitory Concentration (MICs) which are increased substantially, often by many orders of magnitude, when the complexes are initially prepared in water rather than DMSO.

  2. Calculating vibrational spectra without determining excited eigenstates: Solving the complex linear equations of damped response theory for vibrational configuration interaction and vibrational coupled cluster states.

    PubMed

    Godtliebsen, Ian H; Christiansen, Ove

    2015-10-07

    It is demonstrated how vibrational IR and Raman spectra can be calculated from damped response functions using anharmonic vibrational wave function calculations, without determining the potentially very many eigenstates of the system. We present an implementation for vibrational configuration interaction and vibrational coupled cluster, and describe how the complex equations can be solved using iterative techniques employing only real trial vectors and real matrix-vector transformations. Using this algorithm, arbitrary frequency intervals can be scanned independent of the number of excited states. Sample calculations are presented for the IR-spectrum of water, Raman spectra of pyridine and a pyridine-silver complex, as well as for the infra-red spectrum of oxazole, and vibrational corrections to the polarizability of formaldehyde.

  3. Calculating vibrational spectra without determining excited eigenstates: Solving the complex linear equations of damped response theory for vibrational configuration interaction and vibrational coupled cluster states

    NASA Astrophysics Data System (ADS)

    Godtliebsen, Ian H.; Christiansen, Ove

    2015-10-01

    It is demonstrated how vibrational IR and Raman spectra can be calculated from damped response functions using anharmonic vibrational wave function calculations, without determining the potentially very many eigenstates of the system. We present an implementation for vibrational configuration interaction and vibrational coupled cluster, and describe how the complex equations can be solved using iterative techniques employing only real trial vectors and real matrix-vector transformations. Using this algorithm, arbitrary frequency intervals can be scanned independent of the number of excited states. Sample calculations are presented for the IR-spectrum of water, Raman spectra of pyridine and a pyridine-silver complex, as well as for the infra-red spectrum of oxazole, and vibrational corrections to the polarizability of formaldehyde.

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

    SciTech Connect

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

    2012-03-15

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

  5. Energy transfer efficiency based on one-and two-photon FRET microscopy differentiates between clustered and random distribution of membrane-bound receptor-ligand complexes

    NASA Astrophysics Data System (ADS)

    Wallrabe, Horst; Elangovan, Masilamani; Burchard, Almut; Barroso, Margarida

    2002-06-01

    We are investigating membrane-based sorting processes in polarized epithelial MDCK cells, which most likely involves membrane microdomains. We have postulated that proteins contained in these microdomains, cluster, and to prove this, we have internalized differently fluorophore labeled pIgA-R ligands in MDCK cells, stably transfected with polymeric IgA receptors (pIgA-R), from opposite plasma membranes. Our previous work showed that these receptor-ligand complexes colocalize in the apical recycling endosome (ARE), underneath the apical plasma membrane. Quantitative one-photon confocal and 2-photon (2-P) FRET microscopy allowed us to calculate energy transfer efficiency (E%). Unquenched donor levels where established based on a novel algorithm, which corrects the FRET contamination of acceptor bleed-through and donor crosstalk. Using different emission filters also confirmed the veracity of the algorithm. 2-P FRET allows the selection of a specific donor wavelength, which does not precipitate acceptor bleed-through, a clear advantage over 1-P confocal microscopy. Results show that E% is independent of acceptor levels, an indication of a clustered distribution, as in random distribution E% rises with increasing acceptor levels. However, E% decreases with increasing donor and donor:acceptor ratio levels, which we have termed 'donor geometric exclusion', where some donors in a cluster block others from interacting with an acceptor. We submit that this is a second indicator for a clustered pattern, because in a random, dispersed situation donors are not likely to be in close proximity to have such an effect. We have developed a model explaining this phenomenon.

  6. Species-richness of the Anopheles annulipes Complex (Diptera: Culicidae) Revealed by Tree and Model-Based Allozyme Clustering Analyses

    DTIC Science & Technology

    2007-01-01

    International and Tropical Health and Nutrition, The University of Queensland , Brisbane, Queensland 4072, Australia Received 24 January 2006; accepted for...s.l. in Australia t.:l 0 0 ’"’l Number Locality name* Longitude Latitude OTU (N) 15% Cluster Kl5fj1 K20 K25 "’i :r., C 1 Basalt R.t 145°46’E 19°37𔄂...groups is given according to separate Bayesian analyses at K = 15, 20 and 25. ~ *Locations by State and Territory are: 1-20 ( Queensland ), 21-39 (New

  7. Structural and functional characterization of an archaeal clustered regularly interspaced short palindromic repeat (CRISPR)-associated complex for antiviral defense (CASCADE).

    PubMed

    Lintner, Nathanael G; Kerou, Melina; Brumfield, Susan K; Graham, Shirley; Liu, Huanting; Naismith, James H; Sdano, Matthew; Peng, Nan; She, Qunxin; Copié, Valérie; Young, Mark J; White, Malcolm F; Lawrence, C Martin

    2011-06-17

    In response to viral infection, many prokaryotes incorporate fragments of virus-derived DNA into loci called clustered regularly interspaced short palindromic repeats (CRISPRs). The loci are then transcribed, and the processed CRISPR transcripts are used to target invading viral DNA and RNA. The Escherichia coli "CRISPR-associated complex for antiviral defense" (CASCADE) is central in targeting invading DNA. Here we report the structural and functional characterization of an archaeal CASCADE (aCASCADE) from Sulfolobus solfataricus. Tagged Csa2 (Cas7) expressed in S. solfataricus co-purifies with Cas5a-, Cas6-, Csa5-, and Cas6-processed CRISPR-RNA (crRNA). Csa2, the dominant protein in aCASCADE, forms a stable complex with Cas5a. Transmission electron microscopy reveals a helical complex of variable length, perhaps due to substoichiometric amounts of other CASCADE components. A recombinant Csa2-Cas5a complex is sufficient to bind crRNA and complementary ssDNA. The structure of Csa2 reveals a crescent-shaped structure unexpectedly composed of a modified RNA-recognition motif and two additional domains present as insertions in the RNA-recognition motif. Conserved residues indicate potential crRNA- and target DNA-binding sites, and the H160A variant shows significantly reduced affinity for crRNA. We propose a general subunit architecture for CASCADE in other bacteria and Archaea.

  8. Complexation of the vulcanization accelerator tetramethylthiuram disulfide and related molecules with zinc compounds including zinc oxide clusters (Zn4O4).

    PubMed

    Steudel, Ralf; Steudel, Yana; Wong, Ming Wah

    2008-01-01

    Zinc chemicals are used as activators in the vulcanization of organic polymers with sulfur to produce elastic rubbers. In this work, the reactions of Zn(2+), ZnMe(2), Zn(OMe)(2), Zn(OOCMe)(2), and the heterocubane cluster Zn(4)O(4) with the vulcanization accelerator tetramethylthiuram disulfide (TMTD) and with the related radicals and anions Me(2)NCS(2)(*), Me(2)NCS(3)(*), Me(2)NCS(2)(-), and Me(2)NCS(3)(-) have been studied by quantum chemical methods at the MP2/6-31+G(2df,p)//B3LYP/6-31+G* level of theory. More than 35 zinc complexes have been structurally characterized and the energies of formation from their components calculated for the first time. The binding energy of TMTD as a bidendate ligand increases in the order ZnMe(2)complexes with the radicals Me(2)NCS(2)(*) and Me(2)NCS(3)(*). Dissociation of the TMTD molecule at the S-S bond on reaction with the Zn(4)O(4) cluster is predicted to be strongly exothermic, in sharp contrast to the endothermic S-S bond dissociation of the free molecule. The same holds for tetramethylthiuram trisulfide (TMTT). Surprisingly, the resulting complexes contain Zn-S as well as S-O bonds. The Zn(4)O(4) nanocluster serves here as a model for bulk zinc oxide used as an activator in rubber vulcanization by sulfur. The further uptake of sulfur atoms by the various complexes from S(8) or TMTD with formation of species derived from the radical Me(2)NCS(3)(*) or the trithiocarbamate anion Me(2)NCS(3)(-) is endothermic for mono- and dinuclear zinc dithiocarbamate (dtc) complexes such as [Zn(dtc)(2)] and [Zn(2)(dtc)(4)], but exothermic in the case of polynuclear zinc oxide species containing bridging ligands as in [Zn(4)O(4)(mu-S(2)CNMe(2))] and [Zn(4)O(4)(mu-dtc)]. Therefore, zinc oxide as a polynuclear species is predicted to promote the formation of trisulfido complexes, which are generally assumed to serve as catalysts for the transfer of

  9. Edge-bridging and face-capping coordination of alkenyl ligands in triruthenium carbonyl cluster complexes derived from hydrazines: synthetic, structural, theoretical, and kinetic studies.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; Fernández-Colinas, José M; García-Granda, Santiago; Martínez-Méndez, Lorena; Pérez-Carreño, Enrique

    2004-12-03

    The reactions of the triruthenium cluster complex [Ru3(mu-H)(mu3-eta2-HNNMe2)(CO)9] (1; H2NNMe2=1,1-dimethylhydrazine) with alkynes (PhC triple bond CPh, HC triple bond CH, MeO2CC triple bond CCO2Me, PhC triple bond CH, MeO2CC triple bond CH, HOMe2CC triple bond CH, 2-pyC triple bond CH) give trinuclear complexes containing edge-bridging and/or face-capping alkenyl ligands. Whereas the edge-bridged products are closed triangular species (three Ru-Ru bonds), the face-capped products are open derivatives (two Ru-Ru bonds). For terminal alkynes, products containing gem (RCCH2) and/or trans (RHCCH) alkenyl ligands have been identified in both edge-bridging and face-capping positions, except for the complex [Ru3(mu3-eta2-HNNMe2)(mu3-eta3-HCCH-2-py)(mu-CO)(CO)7], which has the two alkenyl H atoms in a cis arrangement. Under comparable reaction conditions (1:1 molar ratio, THF at reflux, time required for the consumption of complex 1), some reactions give a single product, but most give mixtures of isomers (not all the possible ones), which were separated. To determine the effect of the hydrazido ligand, the reactions of [Ru3(mu-H)(mu3-eta2-MeNNHMe)(CO)9] (2; HMeNNHMe=1,2-dimethylhydrazine) with PhC triple bond CPh, PhC triple bond CH, and HC triple bond CH were also studied. For edge-bridged alkenyl complexes, the Ru--Ru edge that is spanned by the alkenyl ligand depends on the position of the methyl groups on the hydrazido ligand. For face-capped alkenyl complexes, the relative orientation of the hydrazido and alkenyl ligands also depends on the position of the methyl groups on the hydrazido ligand. A kinetic analysis of the reaction of 1 with PhC[triple chemical bond]CPh revealed that the reaction follows an associative mechanism, which implies that incorporation of the alkyne in the cluster is rate-limiting and precedes the release of a CO ligand. X-ray diffraction, IR and NMR spectroscopy, and calculations of minimum-energy structures by DFT methods were used to

  10. Characterizing the intrinsic stability of gas-phase clusters of transition metal complex dianions with alkali metal counterions: counterion perturbation of multiply charged anions.

    PubMed

    Burke, Ruth M; Boxford, William E; Dessent, Caroline E H

    2007-02-14

    The authors report the gas-phase generation and characterization of a series of cation-dianion clusters, e.g., M(+).PtCl(6) (2-), M(+).PtCl(4) (2-), M(+).Pt(CN)(6) (2-), and M(+).Pd(CN)(4) (2-), where M(+)=Na(+),K(+),Rb(+), as model systems for investigating gas-phase contact ionpairs. Low-energy collisional excitation of these systems isolated within a quadrupole ion trap reveals that the fragmentation products are determined by the dianion and are independent of the counterion. This indicates that cation-dianion clusters represent gaseous ion-pair complexes, in line with recent findings for K(+).Pt(CN)(n) (2-), n=4,6 [Burke et al., J. Chem. Phys. 125, 021105 (2006)]. The relative fragmentation energies of several cation-dianion systems are obtained as a function of the counterion to explore the nature of ion-pair binding. For most of the systems studied, e.g., M(+).PtCl(6) (2-), the fragmentation energy increases as the cation size decreases, in line with a simple electrostatic description of the cation-dianion binding. However, the M(+).Pt(CN)(4) (2-) clusters displayed the reverse trend with the fragmentation energy increasing as the cation size increases. Density functional theory calculations of the cation-dianion fragmentation potential energy surfaces reveal the existence of a novel double-minima surface, separated by a repulsive Coulomb barrierlike feature at short range. The experimentally observed trends in the fragmentation energies can be fully understood with reference to the computed surfaces, hence providing strong support for the existence of the double-minima surface.

  11. Kinetics of excited states of pigment clusters in solubilized light-harvesting complex II: photon density-dependent fluorescence yield and transmittance.

    PubMed Central

    Schödel, R; Hillmann, F; Schrötter, T; Voigt, J; Irrgang, K D; Renger, G

    1996-01-01

    Relative fluorescence yield, phi F, and transmittance, T, were measured in solubilized light-harvesting complex II (LHCII) as a function of photon density, Ip, of monochromatic 645-nm laser pulses (duration: approximately 2.5 ns). Special efforts were made in constructing an optical set-up that allows the accurate determination of the fluorescence from an area of constant Ip, phi F(Ip) starts to decline at approximately 10(14) and drops to values below 0.01% at maximum Ip (approximately 10(19) photons cm-2 pulse-1). T(Ip) decreases only slightly at photon densities of approximately 10(15) but increases steeply at values of > 10(17) photons cm-2 pulse-1. The interpretation of the phi F(Ip) data using the saturation limit of Mauzerall's multiple hit model leads to a unit size of about 10-15 chlorophyll molecules. One interpretation is to attribute this result to a very fast exciton-exciton annihilation of multiple excited states generated within this small domain. Alternatively, based on the assumption that delocalized cluster states within the monomeric/trimeric subunit of LHCII exist, the results can be consistently described by a kinetic model comprising ground, monoexcitonic, and biexcitonic states of clusters and a triplet state that is quenched by carotenoids in LHCII. Within the framework of this model the annihilation of multiple excitations is explained as ultrafast radiationless relaxation of higher excited cluster states. Comparative measurements in diluted acetonic Chl a solution are consistently described by the depletion of the ground state, taking the absorption cross section at the used wavelength. Images FIGURE 1 PMID:8968606

  12. Cluster Headache

    MedlinePlus

    Cluster headache Overview By Mayo Clinic Staff Cluster headaches, which occur in cyclical patterns or clusters, are one of the most painful types of headache. A cluster headache commonly awakens you ...

  13. Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: Theory, implementation, and examples

    SciTech Connect

    Bravaya, Ksenia B.; Zuev, Dmitry; Epifanovsky, Evgeny; Krylov, Anna I.

    2013-03-28

    Theory and implementation of complex-scaled variant of equation-of-motion coupled-cluster method for excitation energies with single and double substitutions (EOM-EE-CCSD) is presented. The complex-scaling formalism extends the EOM-EE-CCSD model to resonance states, i.e., excited states that are metastable with respect to electron ejection. The method is applied to Feshbach resonances in atomic systems (He, H{sup -}, and Be). The dependence of the results on one-electron basis set is quantified and analyzed. Energy decomposition and wave function analysis reveal that the origin of the dependence is in electron correlation, which is essential for the lifetime of Feshbach resonances. It is found that one-electron basis should be sufficiently flexible to describe radial and angular electron correlation in a balanced fashion and at different values of the scaling parameter, {theta}. Standard basis sets that are optimized for not-complex-scaled calculations ({theta} = 0) are not sufficiently flexible to describe the {theta}-dependence of the wave functions even when heavily augmented by additional sets.

  14. Complex-scaled equation-of-motion coupled-cluster method with single and double substitutions for autoionizing excited states: theory, implementation, and examples.

    PubMed

    Bravaya, Ksenia B; Zuev, Dmitry; Epifanovsky, Evgeny; Krylov, Anna I

    2013-03-28

    Theory and implementation of complex-scaled variant of equation-of-motion coupled-cluster method for excitation energies with single and double substitutions (EOM-EE-CCSD) is presented. The complex-scaling formalism extends the EOM-EE-CCSD model to resonance states, i.e., excited states that are metastable with respect to electron ejection. The method is applied to Feshbach resonances in atomic systems (He, H(-), and Be). The dependence of the results on one-electron basis set is quantified and analyzed. Energy decomposition and wave function analysis reveal that the origin of the dependence is in electron correlation, which is essential for the lifetime of Feshbach resonances. It is found that one-electron basis should be sufficiently flexible to describe radial and angular electron correlation in a balanced fashion and at different values of the scaling parameter, θ. Standard basis sets that are optimized for not-complex-scaled calculations (θ = 0) are not sufficiently flexible to describe the θ-dependence of the wave functions even when heavily augmented by additional sets.

  15. Accounting for interactions and complex inter-subject dependency in estimating treatment effect in cluster randomized trials with missing outcomes

    PubMed Central

    Prague, Melanie; Wang, Rui; Stephens, Alisa; Tchetgen Tchetgen, Eric; DeGruttola, Victor

    2016-01-01

    Summary Semi-parametric methods are often used for the estimation of intervention effects on correlated outcomes in cluster-randomized trials (CRTs). When outcomes are missing at random (MAR), Inverse Probability Weighted (IPW) methods incorporating baseline covariates can be used to deal with informative missingness. Also, augmented generalized estimating equations (AUG) correct for imbalance in baseline covariates but need to be extended for MAR outcomes. However, in the presence of interactions between treatment and baseline covariates, neither method alone produces consistent estimates for the marginal treatment effect if the model for interaction is not correctly specified. We propose an AUG-IPW estimator that weights by the inverse of the probability of being a complete case and allows different outcome models in each intervention arm. This estimator is doubly robust (DR), it gives correct estimates whether the missing data process or the outcome model is correctly specified. We consider the problem of covariate interference which arises when the outcome of an individual may depend on covariates of other individuals. When interfering covariates are not modeled, the DR property prevents bias as long as covariate interference is not present simultaneously for the outcome and the missingness. An R package is developed implementing the proposed method. An extensive simulation study and an application to a CRT of HIV risk reduction-intervention in South Africa illustrate the method. PMID:27060877

  16. Influence of Single Skimmer Versus Dual Funnel Transfer on the Appearance of ESI-Generated LiCl Cluster/ß-Cyclodextrin Inclusion Complexes

    NASA Astrophysics Data System (ADS)

    Kellner, Ina D.; Drewello, Thomas

    2015-08-01

    Singly and doubly charged adducts of LiCl with β-cyclodextrin (βCD) of the type (βCD)(LiCl)nLi+ and (βCD)2(LiCl)pLi2 2+ were studied using electrospray ionization mass spectrometry (ESI-MS). Insight into their structural composition was gained by analysis of their collision-induced dissociation (CID) mass spectra. The conditions the ions experience in the transfer region interfacing the ESI source and the mass analyzer were found to have a marked influence on the nature of the detected ions. In one instrument incorporating a single skimmer, individually attached LiCl ion pairs were observed, whereas the dual funnel ion guides of the second instrument allow the detection of previously unknown labile inclusion complexes of (LiCl)n clusters in βCD.

  17. High-nuclearity ruthenium carbonyl cluster complexes derived from 2-amino-6-methylpyridine: synthesis of nonanuclear derivatives containing mu4- and mu5-oxo ligands.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; García-Alvarez, Pablo; Miguel, Daniel

    2006-07-24

    Nonanuclear cluster complexes [Ru9(mu3-H)2(mu-H)(mu5-O)(mu4-ampy)(mu3-Hampy)(CO)21] (4) (H2ampy = 2-amino-6-methylpyridine), [Ru9(mu5-O)2(mu4-ampy)(mu3-Hampy)2(mu-CO)(CO)20] (5), [Ru9(mu5-O)2(mu4-ampy)(mu3-Hampy)2(mu-CO)2(CO)19] (6), and [Ru9(mu4-O)(mu5-O)(mu4-ampy)(mu3-Hampy)(mu-Hampy)(mu-CO)(CO)19] (7), together with the known hexanuclear [Ru6(mu3-H)2(mu5-ampy)(mu-CO)2(CO)14] (2) and the novel pentanuclear [Ru5(mu4-ampy)(2)(mu-CO)(CO)12] (3) complexes, are products of the thermolysis of [Ru3(mu-H)(mu3-Hampy)(CO)9] (1) in decane at 150 degrees C. Two different and very unusual quadruply bridging coordination modes have been observed for the ampy ligand. Compounds 4-7 also feature one (4) or two (5-7) bridging oxo ligands. With the exception of one of the oxo ligands of 7, which is in a distorted tetrahedral environment, the remaining oxo ligands of 4-7 are surrounded by five metal atoms. In carbonyl metal clusters, quadruply bridging oxo ligands are very unusual, whereas quintuply bridging oxo ligands are unprecedented. By using 18O-labeled water, we have unambiguously established that these oxo ligands arise from water.

  18. A multifrequency study of the active star-forming complex NGC 6357 - I. Interstellar structures linked to the open cluster Pis 24

    NASA Astrophysics Data System (ADS)

    Cappa, C. E.; Barbá, R.; Duronea, N. U.; Vasquez, J.; Arnal, E. M.; Goss, W. M.; Fernández Lajús, E.

    2011-08-01

    We investigate the distribution of gas (ionized, neutral atomic and molecular) and interstellar dust in the complex star-forming region NGC 6357 with the goal of studying the interplay between the massive stars in the open cluster Pis 24 and the surrounding interstellar matter. Our study of the distribution of the ionized gas is based on narrow-band Hα, [S II]and [O III] images obtained with the Curtis-Schmidt Camera at CTIO, Chile, and on radio continuum observations at 1465 MHz taken with the VLA with a synthesized beam of 40 arcsec. The distribution of the molecular gas is analysed using 12CO(1-0) data obtained with the NANTEN radiotelescope, Chile (angular resolution = 2.7 arcmin). The interstellar dust distribution was studied using mid-infrared data from the GLIMPSE survey and far-infrared observations from IRAS. NGC 6357 consists of a large ionized shell and a number of smaller optical nebulosities. The optical, radio continuum, and near- and mid-IR images delineate the distributions of the ionized gas and interstellar dust in the H II regions and in previously unknown wind-blown bubbles linked to the massive stars in Pis 24 revealing surrounding photodissociation regions. The CO line observations allowed us to identify the molecular counterparts of the ionized structures in the complex and to confirm the presence of photodissociation regions. The action of the WR star HD 157504 on the surrounding gas was also investigated. The molecular mass in the complex is estimated to be (4 ± 2) × 105 M⊙. The mean electron densities derived from the radio data suggest electron densities >200 cm-3, indicating that NGC 6357 is a complex formed in a region of high ambient density. The known massive stars in Pis 24 and a number of newly inferred massive stars are mainly responsible for the excitation and photodissociation of the parental molecular cloud.

  19. A rare tetranuclear thorium(IV) μ4 -oxo cluster and dinuclear thorium(IV) complex assembled by carbon-oxygen bond activation of 1,2-dimethoxyethane (DME).

    PubMed

    Travia, Nicholas E; Scott, Brian L; Kiplinger, Jaqueline L

    2014-12-15

    The synthesis and X-ray crystal structure of two new multinuclear thorium complexes are reported. The tetranuclear μ4 -oxo cluster complex Th4 (μ4 -O)(μ-Cl)2 I6 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]6 and the dinuclear complex Th2 I5 [κ(2) (O,O')-μ-O(CH2 )2 OCH3 ]3 (DME) (DME=dimethoxyethane) are formed by CO bond activation of 1,2-dimethoxyethane (DME) mediated by thorium iodide complexes.

  20. Comparison of CBS-QB3, CBS-APNO, G2, and G3 thermochemical predictions with experiment for formation of ionic clusters of hydronium and hydroxide ions complexed with water.

    PubMed

    Pickard, Frank C; Pokon, Emma K; Liptak, Matthew D; Shields, George C

    2005-01-08

    The GAUSSIAN 2, GAUSSIAN 3, complete basis set-QB3, and complete basis set-APNO methods have been used to calculate DeltaH( composite function) and DeltaG( composite function) values for ionic clusters of hydronium and hydroxide ions complexed with water. Results for the clusters H3O+(H2O)n and OH-(H2O)n, where n=1-4 are reported in this paper, and compared against experimental values contained in the National Institutes of Standards and Technology (NIST) database. Agreement with experiment is excellent for the three ab initio methods for formation of these clusters. The high accuracy of these methods makes them reliable for calculating energetics for the formation of ionic clusters containing water. In addition this allows them to serve as a valuable check on the accuracy of experimental data reported in the NIST database, and makes them useful tools for addressing unresolved issues in atmospheric chemistry.

  1. Electronic Structure of the Mn[subscript 4]Ca Cluster in the Oxygen-Evolving Complex of Photosystem II Studied by Resonant Inelastic X-Ray Scattering

    SciTech Connect

    Yano, Junko; Pushkar, Yulia; Messinger, Johannes; Bergmann, Uwe; Glatzel, Pieter; Yachandra, Vittal K.

    2007-11-12

    Oxygen-evolving complex (Mn{sub 4}Ca cluster) of Photosystem II cycles through five intermediate states (S{sub i}-states, i = 0-4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn{sub 4}(III{sub 2},IV{sub 2}) and Mn{sub 4}(III,IV{sub 3}) for S{sub 1} and S{sub 2} states, while it is still controversial for the S{sub 0} and S{sub 3} states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn{sub 4}Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra simultaneously. The second energy dimension separates the pre-edge (1s to 3d) transitions from the main K-edge (1s to 4p), and thus more precise analysis is possible. The 1s2p RIXS final state electron configuration along the energy transfer axis is identical to conventional L-edge absorption spectroscopy and the RIXS spectra are therefore sensitive to the metal spin state. We have collected data from PS II samples in the each of the S-states and compared them with data from various inorganic Mn complexes. The spectral changes in the Mn 1s2p{sub 3/2} RIXS spectra between the S-states are small compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S{sub 0} to S{sub 1}, and S{sub 1} to S{sub 2} transitions is twice as large as that during the S{sub 2} to S{sub 3} transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms. The RIXS spectra of S{sub 0} and S{sub 3

  2. Electronic Structure of the Mn(4)Ca Cluster in the Oxygen-Evolving Complex of Photosystem Ii Studied By Resonant Inelastic X-Ray Scattering

    SciTech Connect

    Yano, J.; Pushkar, Y.; Messinger, J.; Bergmann, U.; Glatzel, P.; Yachandra, V.K.

    2009-06-04

    Oxygen-evolving complex (Mn{sub 4}Ca cluster) of Photosystem II cycles through five intermediate states (S{sub i}-states, i=0--4) before a molecule of dioxygen is released. During the S-state transitions, electrons are extracted from the OEC, either from Mn or alternatively from a Mn ligand. The oxidation state of Mn is widely accepted as Mn{sub 4}(III{sub 2},IV{sub 2}) and Mn{sub 4}(III,IV{sub 3}) for S{sub 1} and S{sub 2} states, while it is still controversial for the S{sub 0} and S{sub 3} states. We used resonant inelastic X-ray scattering (RIXS) to study the electronic structure of Mn{sub 4}Ca complex in the OEC. The RIXS data yield two-dimensional plots that provide a significant advantage by obtaining both K-edge pre-edge and L-edge-like spectra simultaneously. The second energy dimension separates the pre-edge (1s to 3d) transitions from the main K-edge (1s to 4p), and thus more precise analysis is possible. The 1s2p RIXS final state electron configuration along the energy transfer axis is identical to conventional L-edge absorption spectroscopy and the RIXS spectra are therefore sensitive to the metal spin state. We have collected data from PS II samples in the each of the S-states and compared them with data from various inorganic Mn complexes. The spectral changes in the Mn 1s2p{sub 3/2} RIXS spectra between the S-states are small compared to those of the oxides of Mn and coordination complexes. The results indicate strong covalency for the electronic configuration in the OEC, and we conclude that the electron is transferred from a strongly delocalized orbital, compared to those in Mn oxides or coordination complexes. The magnitude for the S{sub 0} to S{sub 1}, and S{sub 1} to S{sub 2} transitions is twice as large as that during the S{sub 2} to S{sub 3} transition, indicating that the electron for this transition is extracted from a highly delocalized orbital with little change in charge density at the Mn atoms. The RIXS spectra of S{sub 0} and S{sub 3

  3. A density functional investigation of thiolate-protected bimetal PdAu(24)(SR)(18)(z) clusters: doping the superatom complex.

    PubMed

    Kacprzak, Katarzyna A; Lehtovaara, Lauri; Akola, Jaakko; Lopez-Acevedo, Olga; Häkkinen, Hannu

    2009-09-07

    Structure, electronic properties, optical absorption and charging properties of methylthiolate-protected bimetal PdAu(24)(SR)(18)(z) (R = Me) clusters with various charge states (-3 complex Au(25)(SR)(18)((-1)) [J. Akola, M. Walter, H. Häkkinen and H. Grönbeck, J. Am. Chem. Soc., 2008, 130, 3756]. The atomic structure of this all-gold complex can be written in a "divide-and-protect" way [H. Häkkinen, M. Walter and H. Grönbeck, J. Phys. Chem. B, 2006, 110, 9927] as Au(13)[Au(2)(SR)(3)](6)((-1)) where 6 v-shaped Au(2)(SR)(3) ligands protect the close-to-icosahedral Au(13) core and where eight delocalized metal electrons, derived from Au(6s) electrons, comprise a stable closed-shell 1S(2)1P(6)"superatom" configuration in the core. We show that the di-anion PdAu(24)(SR)(18)((-2)) is a corresponding eight-electron closed-shell species whereas the clusters PdAu(24)(SR)(18)(z), -1

  4. CLUSTER CHEMISTRY

    SciTech Connect

    Muetterties, Earl L.

    1980-05-01

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

  5. Shaping a high-mass star-forming cluster through stellar feedback. The case of the NGC 7538 IRS 1-3 complex

    NASA Astrophysics Data System (ADS)

    Frau, P.; Girart, J. M.; Zhang, Q.; Rao, R.

    2014-07-01

    Context. NGC 7538 IRS 1-3 is a high-mass star-forming cluster with several detected dust cores, infrared sources, (ultra)compact H II regions, molecular outflows, and masers. In such a complex environment, interactions and feedback among the embedded objects are expected to play a major role in the evolution of the region. Aims: We study the dust, kinematic, and polarimetric properties of the NGC 7538 IRS 1-3 region to investigate the role of the different forces in the formation and evolution of high-mass star-forming clusters. Methods: We performed SMA high angular resolution observations at 880 μm with the compact configuration. We developed the RATPACKS code to generate synthetic velocity cubes from models of choice to be compared to the observational data. To quantify the stability against gravitational collapse we developed the "mass balance" analysis that accounts for all the energetics on core scales. Results: We detect 14 dust cores from 3.5 M⊙ to 37 M⊙ arranged in two larger scale structures: a central bar and a filamentary spiral arm. The spiral arm presents large-scale velocity gradients in H13CO+ 4-3 and C17O 3-2, and magnetic field segments aligned well to the dust main axis. The velocity gradient is reproduced well by a spiral arm expanding at 9 km s-1 with respect to the central core MM1, which is known to power a large precessing outflow. The energy of the outflow is comparable to the spiral-arm kinetic energy, which dominates gravitational and magnetic energies. In addition, the dynamical ages of the outflow and spiral arm are comparable. On core scales, those embedded in the central bar seem to be unstable against gravitational collapse and prone to forming high-mass stars, while those in the spiral arm have lower masses that seem to be supported by non-thermal motions and magnetic fields. Conclusions: The NGC 7538 IRS 1-3 cluster seems to be dominated by protostellar feedback. The dusty spiral arm appears to be formed in a snowplow fashion

  6. Effectiveness of a complex intervention in reducing the prevalence of smoking among adolescents: study design of a cluster-randomized controlled trial

    PubMed Central

    2014-01-01

    Background The likelihood of an adolescent taking up smoking may be influenced by his or her society, school and family. Thus, changes in the immediate environment may alter a young person’s perception of smoking. Methods/Design The proposed multi-center, cluster-randomized controlled trial will be stratified by the baseline prevalence of smoking in schools. Municipalities with fewer than 100,000 inhabitants will be randomly assigned to a control or intervention group. One secondary school will be randomly selected from each municipality. These schools will be randomized to two groups: the students of one will receive any existing educational course regarding smoking, while those of the other school will receive a four-year, class-based curriculum intervention (22 classroom lessons) aimed at reinforcing a smoke-free school policy and encouraging smoking cessation in parents, pupils, and teachers. The intervention will also include annual meetings with parents and efforts to empower adolescents to change the smoking-related attitudes and behaviors in their homes, classrooms and communities. We will enroll children aged 12-13 years as they enter secondary school during two consecutive school years (to obtain sufficient enrolled subjects). We will follow them for five years, until two years after they leave secondary school. All external evaluators and analysts will be blinded to school allocation. The aim of this study is to analyze the effectiveness of a complex intervention in reducing the prevalence of smoking in the third year of compulsory secondary education (ESO) and two years after secondary school, when the participants are 14-15 and 17-18 years old, respectively. Discussion Most interventions aimed at preventing smoking among adolescents yield little to no positive long-term effects. This clinical trial will analyze the effectiveness of a complex intervention aimed at reducing the incidence and prevalence of smoking in this vulnerable age group. Trial

  7. Human Lin28 Forms a High-Affinity 1:1 Complex with the 106~363 Cluster miRNA miR-363

    PubMed Central

    2016-01-01

    Lin28A is a post-transcriptional regulator of gene expression that interacts with and negatively regulates the biogenesis of let-7 family miRNAs. Recent data suggested that Lin28A also binds the putative tumor suppressor miR-363, a member of the 106~363 cluster of miRNAs. Affinity for this miRNA and the stoichiometry of the protein–RNA complex are unknown. Characterization of human Lin28’s interaction with RNA has been complicated by difficulties in producing stable RNA-free protein. We have engineered a maltose binding protein fusion with Lin28, which binds let-7 miRNA with a Kd of 54.1 ± 4.2 nM, in agreement with previous data on a murine homologue. We show that human Lin28A binds miR-363 with a 1:1 stoichiometry and with a similar, if not higher, affinity (Kd = 16.6 ± 1.9 nM). Further analysis suggests that the interaction of the N-terminal cold shock domain of Lin28A with RNA is salt-dependent, supporting a model in which the cold shock domain allows the protein to sample RNA substrates through transient electrostatic interactions. PMID:27559824

  8. Unusual self-assembled 1D tape of tetramers and water-nitrate clusters trapped in a zinc(II) complex: Synthesis, characterization, luminescence and catalytic properties

    NASA Astrophysics Data System (ADS)

    Ma, De-Yun; Guo, Hai-Fu; Dong, Ji; Xu, Jun

    2013-12-01

    Unusual tetramers and water-nitrate clusters have been observed in a mononuclear zinc(II) complex of [Zn(4-cpa)(phen)2(H2O)]·(H2O)·(NO3)] (1), (4-Hcpa = 4-chlorophenoxyacetic acid, phen = 1,10-phenanthroline), which was synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffraction, UV-vis absorption spectra and single-crystal X-ray diffraction. The crystal structure analysis of 1, reveals that the nitrate anions, water molecules and carboxylate oxygen atoms (O3) pack to form a one-dimensional infinite tape parallel to the c-axis. The uncoordinated carboxylate oxygen atoms (O3) of 4-cpa ligands, water molecules and nitrate anions interact via hydrogen bonds and extend 1 into a water-anion-cation tape, which are finally connected into a 3D supramolecular structure via π⋯π stacking interactions. Excitation (λex = 310 nm) and luminescence data observed at room temperature show that 1 emits bright blue fluorescence. Moreover, 1 has a remarkable activity for degradation of methyl orange in a photo-assisted Fenton-like process.

  9. Designing of the Information Advising System to Assess the Potential of Creation and Development of Cluster Agglomeration in the Industrial Complex of the Region

    NASA Astrophysics Data System (ADS)

    Averchenkova, E. E.; Averchenkov, A. V.; Kulagina, N. A.

    2017-01-01

    The theoretical aspects of creation of the information advising system to assess the potential of development of the cluster agglomeration are described in this article. The algorithm provided in the article estimates possibilities of creation and development of the regional industrial cluster agglomeration. This article describes the possible use of the information advising system of the evaluation and diagnostic type in making managerial decisions by the participants of the technology innovation cluster.

  10. Functional Dynamics Revealed by the Structure of the SufBCD Complex, a Novel ATP-binding Cassette (ABC) Protein That Serves as a Scaffold for Iron-Sulfur Cluster Biogenesis*

    PubMed Central

    Hirabayashi, Kei; Yuda, Eiki; Tanaka, Naoyuki; Katayama, Sumie; Iwasaki, Kenji; Matsumoto, Takashi; Kurisu, Genji; Outten, F. Wayne; Fukuyama, Keiichi; Takahashi, Yasuhiro; Wada, Kei

    2015-01-01

    ATP-binding cassette (ABC)-type ATPases are chemomechanical engines involved in diverse biological pathways. Recent genomic information reveals that ABC ATPase domains/subunits act not only in ABC transporters and structural maintenance of chromosome proteins, but also in iron-sulfur (Fe-S) cluster biogenesis. A novel type of ABC protein, the SufBCD complex, functions in the biosynthesis of nascent Fe-S clusters in almost all Eubacteria and Archaea, as well as eukaryotic chloroplasts. In this study, we determined the first crystal structure of the Escherichia coli SufBCD complex, which exhibits the common architecture of ABC proteins: two ABC ATPase components (SufC) with function-specific components (SufB-SufD protomers). Biochemical and physiological analyses based on this structure provided critical insights into Fe-S cluster assembly and revealed a dynamic conformational change driven by ABC ATPase activity. We propose a molecular mechanism for the biogenesis of the Fe-S cluster in the SufBCD complex. PMID:26472926

  11. Rhenium Complexes and Clusters Supported on c-Al2O3: Effects of Rhenium Oxidation State and Rhenium Cluster Size on Catalytic Activity for n-butane Hydrogenolysis

    SciTech Connect

    Lobo Lapidus, R.; Gates, B

    2009-01-01

    Supported metals prepared from H{sub 3}Re{sub 3}(CO){sub 12} on {gamma}-Al{sub 2}O{sub 3} were treated under conditions that led to various rhenium structures on the support and were tested as catalysts for n-butane conversion in the presence of H{sub 2} in a flow reactor at 533 K and 1 atm. After use, two samples were characterized by X-ray absorption edge positions of approximately 5.6 eV (relative to rhenium metal), indicating that the rhenium was cationic and essentially in the same average oxidation state in each. But the Re-Re coordination numbers found by extended X-ray absorption fine structure spectroscopy (2.2 and 5.1) show that the clusters in the two samples were significantly different in average nuclearity despite their indistinguishable rhenium oxidation states. Spectra of a third sample after catalysis indicate approximately Re{sub 3} clusters, on average, and an edge position of 4.5 eV. Thus, two samples contained clusters approximated as Re{sub 3} (on the basis of the Re-Re coordination number), on average, with different average rhenium oxidation states. The data allow resolution of the effects of rhenium oxidation state and cluster size, both of which affect the catalytic activity; larger clusters and a greater degree of reduction lead to increased activity.

  12. A Cluster of Four Homologous Small RNAs Modulates C1 Metabolism and the Pyruvate Dehydrogenase Complex in Rhodobacter sphaeroides under Various Stress Conditions

    PubMed Central

    Billenkamp, Fabian; Peng, Tao; Berghoff, Bork A.

    2015-01-01

    ABSTRACT In bacteria, regulatory RNAs play an important role in the regulation and balancing of many cellular processes and stress responses. Among these regulatory RNAs, trans-encoded small RNAs (sRNAs) are of particular interest since one sRNA can lead to the regulation of multiple target mRNAs. In the purple bacterium Rhodobacter sphaeroides, several sRNAs are induced by oxidative stress. In this study, we focused on the functional characterization of four homologous sRNAs that are cotranscribed with the gene for the conserved hypothetical protein RSP_6037, a genetic arrangement described for only a few sRNAs until now. Each of the four sRNAs is characterized by two stem-loops that carry CCUCCUCCC motifs in their loops. They are induced under oxidative stress, as well as by various other stress conditions, and were therefore renamed here sRNAs CcsR1 to CcsR4 (CcsR1–4) for conserved CCUCCUCCC motif stress-induced RNAs 1 to 4. Increased CcsR1–4 expression decreases the expression of genes involved in C1 metabolism or encoding components of the pyruvate dehydrogenase complex either directly by binding to their target mRNAs or indirectly. One of the CcsR1–4 target mRNAs encodes the transcriptional regulator FlhR, an activator of glutathione-dependent methanol/formaldehyde metabolism. Downregulation of this glutathione-dependent pathway increases the pool of glutathione, which helps to counteract oxidative stress. The FlhR-dependent downregulation of the pyruvate dehydrogenase complex reduces a primary target of reactive oxygen species and reduces aerobic electron transport, a main source of reactive oxygen species. Our findings reveal a previously unknown strategy used by bacteria to counteract oxidative stress. IMPORTANCE Phototrophic organisms have to cope with photo-oxidative stress due to the function of chlorophylls as photosensitizers for the formation of singlet oxygen. Our study assigns an important role in photo-oxidative stress resistance to a

  13. Effectiveness of a primary care based complex intervention to promote self-management in patients presenting psychiatric symptoms: study protocol of a cluster-randomized controlled trial

    PubMed Central

    2014-01-01

    Background Anxiety, Depression and Somatoform (ADSom) disorders are highly prevalent in primary care. Managing these disorders is time-consuming and requires strong commitment on behalf of the General Practitioners (GPs). Furthermore, the management of these patients is restricted by the high patient turnover rates in primary care practices, especially in the German health care system. In order to address this problem, we implement a complex, low-threshold intervention by an Advanced Practice Nurse (APN) using a mixture of case management and counseling techniques to promote self-management in these patients. Here we present the protocol of the “Self-Management Support for Anxiety, Depression and Somatoform Disorders in Primary Care” (SMADS)-Study. Methods/Design The study is designed as a cluster-randomized controlled trial, comparing an intervention and a control group of 10 primary care practices in each case. We will compare the effectiveness of the intervention applied by an APN with usual GP-care. A total of 340 participants will be enrolled in the study, 170 in either arm. We use the Patient Health Questionnaire-German version (PHQ-D) as a screening tool for psychiatric symptoms, including patients with a score above 5 on any of the three symptom scales. The primary outcome is self-efficacy, measured by the General Self-Efficacy Scale (GSE), here used as a proxy for self-management. As secondary outcomes we include the PHQ-D symptom load and questionnaires regarding coping with illness and health related quality of life. Outcome assessments will be applied 8 weeks and 12 months after the baseline assessment. Discussion The SMADS-study evaluates a complex, low threshold intervention for ambulatory patients presenting ADSom-symptoms, empowering them to better manage their condition, as well as improving their motivation to engage in self-help and health-seeking behaviour. The benefit of the intervention will be substantiated, when patients can enhance

  14. The food choice at work study: effectiveness of complex workplace dietary interventions on dietary behaviours and diet-related disease risk - study protocol for a clustered controlled trial

    PubMed Central

    2013-01-01

    Background Dietary behaviour interventions have the potential to reduce diet-related disease. Ample opportunity exists to implement these interventions in the workplace. The overall aim is to assess the effectiveness and cost-effectiveness of complex dietary interventions focused on environmental dietary modification alone or in combination with nutrition education in large manufacturing workplace settings. Methods/design A clustered controlled trial involving four large multinational manufacturing workplaces in Cork will be conducted. The complex intervention design has been developed using the Medical Research Council’s framework and the National Institute for Health and Clinical Excellence (NICE) guidelines and will be reported using the TREND statement for the transparent reporting of evaluations with non-randomized designs. It will draw on a soft paternalistic “nudge” theoretical perspective. Nutrition education will include three elements: group presentations, individual nutrition consultations and detailed nutrition information. Environmental dietary modification will consist of five elements: (a) restriction of fat, saturated fat, sugar and salt, (b) increase in fibre, fruit and vegetables, (c) price discounts for whole fresh fruit, (d) strategic positioning of healthier alternatives and (e) portion size control. No intervention will be offered in workplace A (control). Workplace B will receive nutrition education. Workplace C will receive nutrition education and environmental dietary modification. Workplace D will receive environmental dietary modification alone. A total of 448 participants aged 18 to 64 years will be selected randomly. All permanent, full-time employees, purchasing at least one main meal in the workplace daily, will be eligible. Changes in dietary behaviours, nutrition knowledge, health status with measurements obtained at baseline and at intervals of 3 to 4 months, 7 to 9 months and 13 to 16 months will be recorded. A process

  15. Architecture of the Yeast Mitochondrial Iron-Sulfur Cluster Assembly Machinery: THE SUB-COMPLEX FORMED BY THE IRON DONOR, Yfh1 PROTEIN, AND THE SCAFFOLD, Isu1 PROTEIN.

    PubMed

    Ranatunga, Wasantha; Gakh, Oleksandr; Galeano, Belinda K; Smith, Douglas Y; Söderberg, Christopher A G; Al-Karadaghi, Salam; Thompson, James R; Isaya, Grazia

    2016-05-06

    The biosynthesis of Fe-S clusters is a vital process involving the delivery of elemental iron and sulfur to scaffold proteins via molecular interactions that are still poorly defined. We reconstituted a stable, functional complex consisting of the iron donor, Yfh1 (yeast frataxin homologue 1), and the Fe-S cluster scaffold, Isu1, with 1:1 stoichiometry, [Yfh1]24·[Isu1]24 Using negative staining transmission EM and single particle analysis, we obtained a three-dimensional reconstruction of this complex at a resolution of ∼17 Å. In addition, via chemical cross-linking, limited proteolysis, and mass spectrometry, we identified protein-protein interaction surfaces within the complex. The data together reveal that [Yfh1]24·[Isu1]24 is a roughly cubic macromolecule consisting of one symmetric Isu1 trimer binding on top of one symmetric Yfh1 trimer at each of its eight vertices. Furthermore, molecular modeling suggests that two subunits of the cysteine desulfurase, Nfs1, may bind symmetrically on top of two adjacent Isu1 trimers in a manner that creates two putative [2Fe-2S] cluster assembly centers. In each center, conserved amino acids known to be involved in sulfur and iron donation by Nfs1 and Yfh1, respectively, are in close proximity to the Fe-S cluster-coordinating residues of Isu1. We suggest that this architecture is suitable to ensure concerted and protected transfer of potentially toxic iron and sulfur atoms to Isu1 during Fe-S cluster assembly.

  16. A Chandra Study of the Rosette Star-forming Complex. III. The NGC 2237 Cluster and the Region's Star Formation History

    NASA Astrophysics Data System (ADS)

    Wang, Junfeng; Feigelson, Eric D.; Townsley, Leisa K.; Broos, Patrick S.; Román-Zúñiga, Carlos G.; Lada, Elizabeth; Garmire, Gordon

    2010-06-01

    We present high spatial resolution Chandra X-ray images of the NGC 2237 young stellar cluster on the periphery of the Rosette Nebula. We detect 168 X-ray sources, 80% of which have stellar counterparts in USNO, Two Micron All Sky Survey, and deep FLAMINGOS images. These constitute the first census of the cluster members with 0.2 <~ M <~ 2 M sun. Star locations in near-infrared color-magnitude diagrams indicate a cluster age around 2 Myr with a visual extinction of 1 <~ AV <~ 3 at 1.4 kpc, the distance of the Rosette Nebula's main cluster NGC 2244. We derive the K-band luminosity function and the X-ray luminosity function of the cluster, which indicate a population ~400-600 stars. The X-ray-selected sample shows a K-excess disk frequency of 13%. The young Class II counterparts are aligned in an arc ~3 pc long suggestive of a triggered formation process induced by the O stars in NGC 2244. The diskless Class III sources are more dispersed. Several X-ray emitting stars are located inside the molecular cloud and around gaseous pillars projecting from the cloud. These stars, together with a previously unreported optical outflow originating inside the cloud, indicate that star formation is continuing at a low level and the cluster is still growing. This X-ray view of young stars on the western side of the Rosette Nebula complements our earlier studies of the central cluster NGC 2244 and the embedded clusters on the eastern side of the Nebula. The large-scale distribution of the clusters and molecular material is consistent with a scenario in which the rich central NGC 2244 cluster formed first, and its expanding H II region triggered the formation of the now-unobscured satellite clusters Rosette Molecular Cloud (RMC) XA and NGC 2237. A large swept-up shell material around the H II region is now in a second phase of collect-and-collapse fragmentation, leading to the recent formation of subclusters. Other clusters deeper in the molecular cloud appear unaffected by the

  17. A CHANDRA STUDY OF THE ROSETTE STAR-FORMING COMPLEX. III. THE NGC 2237 CLUSTER AND THE REGION'S STAR FORMATION HISTORY

    SciTech Connect

    Wang Junfeng; Feigelson, Eric D.; Townsley, Leisa K.; Broos, Patrick S.; Garmire, Gordon; Roman-Zuniga, Carlos G.; Lada, Elizabeth

    2010-06-10

    We present high spatial resolution Chandra X-ray images of the NGC 2237 young stellar cluster on the periphery of the Rosette Nebula. We detect 168 X-ray sources, 80% of which have stellar counterparts in USNO, Two Micron All Sky Survey, and deep FLAMINGOS images. These constitute the first census of the cluster members with 0.2 {approx}< M {approx}< 2 M {sub sun}. Star locations in near-infrared color-magnitude diagrams indicate a cluster age around 2 Myr with a visual extinction of 1 {approx}< A{sub V} {approx}< 3 at 1.4 kpc, the distance of the Rosette Nebula's main cluster NGC 2244. We derive the K-band luminosity function and the X-ray luminosity function of the cluster, which indicate a population {approx}400-600 stars. The X-ray-selected sample shows a K-excess disk frequency of 13%. The young Class II counterparts are aligned in an arc {approx}3 pc long suggestive of a triggered formation process induced by the O stars in NGC 2244. The diskless Class III sources are more dispersed. Several X-ray emitting stars are located inside the molecular cloud and around gaseous pillars projecting from the cloud. These stars, together with a previously unreported optical outflow originating inside the cloud, indicate that star formation is continuing at a low level and the cluster is still growing. This X-ray view of young stars on the western side of the Rosette Nebula complements our earlier studies of the central cluster NGC 2244 and the embedded clusters on the eastern side of the Nebula. The large-scale distribution of the clusters and molecular material is consistent with a scenario in which the rich central NGC 2244 cluster formed first, and its expanding H II region triggered the formation of the now-unobscured satellite clusters Rosette Molecular Cloud (RMC) XA and NGC 2237. A large swept-up shell material around the H II region is now in a second phase of collect-and-collapse fragmentation, leading to the recent formation of subclusters. Other clusters deeper

  18. Cluster headache

    MedlinePlus

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

  19. Meaningful Clusters

    SciTech Connect

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

    2004-05-26

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

  20. Structures and magnetic properties of an antiferromagnetically coupled polymeric copper(II) complex and ferromagnetically coupled hexanuclear nickel(II) clusters.

    PubMed

    Tandon, Santokh S; Bunge, Scott D; Sanchiz, Joaquin; Thompson, Laurence K

    2012-03-05

    Reactions between 2,6-diformyl-4-methylphenol (DFMF) and tris(hydroxymethyl) aminomethane (THMAM = H(3)L2) in the presence of copper(II) salts, CuX(2) (X = CH(3)CO(2)(-), BF(4)(-), ClO(4)(-), Cl(-), NO(3)(-)) and Ni(CH(3)CO(2))(2) or Ni(ClO(4))(2)/NaC(6)H(5)CO(2), sodium azide (NaN(3)), and triethylamine (TEA), in one pot self-assemble giving a coordination polymer consisting of repeating pentanuclear copper(II) clusters {[Cu(2)(H(5)L(2-))(μ-N(3))](2)[Cu(N(3))(4)]·2CH(3)OH}(n) (1) and hexanuclear Ni(II) complexes [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(CH(3)CO(2))(2)]·6C(3)H(7)NO·C(2)H(5)OH (2) and [Ni(6)(H(3)L1(-))(2)(HL2(2-))(2)(μ-N(3))(4)(C(6)H(5)CO(2))(2)]·3C(3)H(7)NO·3H(2)O·CH(3)OH (3). In 1, H(5)L(2-) and in 2 and 3 H(3)L1(-) and HL2(2-) represent doubly deprotonated, singly deprotonated, and doubly deprotonated Schiff-base ligands H(7)L and H(4)L1 and a tripodal ligand H(3)L2, respectively. 1 has a novel double-stranded ladder-like structure in which [Cu(N(3))(4)](2-) anions link single chains comprised of dinuclear cationic subunits [Cu(2)(H(5)L(2-))(μ-N(3))](+), forming a 3D structure of interconnected ladders through H bonding. Nickel(II) clusters 2 and 3 have very similar neutral hexanuclear cores in which six nickel(II) ions are bonded to two H(4)L1, two H(3)L2, four μ-azido, and two μ-CH(3)CO(2)(-)/μ-C(6)H(5)CO(2)(-) ligands. In each structure two terminal dinickel (Ni(2)) units are connected to the central dinickel unit through four doubly bridging end-on (EO) μ-azido and four triply bridging μ(3)-methoxy bridges organizing into hexanuclear units. In each terminal dinuclear unit two nickel centers are bridged through one μ-phenolate oxygen from H(3)L1(-), one μ(3)-methoxy oxygen from HL2(2-), and one μ-CH(3)CO(2)(-) (2)/μ-C(6)H(5)CO(2)(-) (3) ion. Bulk magnetization measurements on 1 show moderately strong antiferromagnetic coupling within the [Cu(2)] building block (J(1) = -113.5 cm(-1)). Bulk magnetization measurements on 2

  1. Photoelectron spectroscopy of molecular clusters

    NASA Astrophysics Data System (ADS)

    Zhang, Xu; Pitts, Jonathan; Zheng, Chaowen; Knee, Joseph L.

    1995-09-01

    High resolution photoelectron spectroscopy is applied to the study of molecular clusters. The primary species studied are fluorene-Arn complexes. Spectroscopy of the neutral S1 state has been performed on clusters as large as n equals 30. In order to study the photoelectron spectra of the clusters size selectively mass analyzed threshold ionization (MATI) is used which is a mass resolved version of the ZEKE technique. MATI spectroscopy has been applied to clusters up to n equals 5. The spectral shifts in the S1 origin and ion threshold are used as a measure of the relative stability of the different clusters. Using previous experimental and theoretical work on related clusters the structures of the clusters are inferred from the observed spectral shifts. In some cases multiple conformations of a particular cluster size are identified.

  2. Charge transfer initiated nitroxyl chemistry on free silver clusters Ag{sub 2-5}{sup-} : size effects and magic complexes.

    SciTech Connect

    Hagen, J.; Socaciu-Sieberg, L. D.; LeRoux, J.; Popolan, D.; Vajda, S.; Bernhardt, T. M.; Woste, L.; Chemistry; Freie Univ.; Univ. Ulm

    2007-01-01

    The reactivity of small silver cluster anions Ag{sub 2--5}- toward nitric oxide and mixtures of nitric oxide with carbon monoxide is investigated under multi-collision conditions in a radio frequency octopole ion trap at temperatures of 100 and 300 K. A strongly cluster size dependent reaction behavior is observed, where reactive fragmentation dominates for clusters with four or fewer atoms and only Ag{sub 5}- is able to form reaction products without dissociation of the metal cluster. The decisive role of charge transfer in the NO bond breakage, NO oxidation, and the formation of free NO{sub 2}{sup -} and N{sub 2}O{sub 4}{sup -} ions, as well as NxO(y>x)-ligands on the silver clusters is discussed. The mass spectrometric data reveal the particular stability of the reaction products AgN{sub 2}O{sub 4}{sup -} and Ag{sub 3}NO{sup -}. The reaction product mass spectra obtained for Ag{sub 5}{sup -} in the presence of NO and CO show the depletion of the NxO(y>x)-ligands on the metal cluster possibly involving the oxidation of CO to CO2.

  3. Stormy weather in galaxy clusters

    PubMed

    Burns

    1998-04-17

    Recent x-ray, optical, and radio observations coupled with particle and gas dynamics numerical simulations reveal an unexpectedly complex environment within clusters of galaxies, driven by ongoing accretion of matter from large-scale supercluster filaments. Mergers between clusters and continuous infall of dark matter and baryons from the cluster periphery produce long-lived "stormy weather" within the gaseous cluster atmosphere-shocks, turbulence, and winds of more than 1000 kilometers per second. This weather may be responsible for shaping a rich variety of extended radio sources, which in turn act as "barometers" and "anemometers" of cluster weather.

  4. 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.

  5. Application of Balanced Scorecard in the Evaluation of a Complex Health System Intervention: 12 Months Post Intervention Findings from the BHOMA Intervention: A Cluster Randomised Trial in Zambia

    PubMed Central

    Mutale, Wilbroad; Stringer, Jeffrey; Chintu, Namwinga; Chilengi, Roma; Mwanamwenge, Margaret Tembo; Kasese, Nkatya; Balabanova, Dina; Spicer, Neil; Lewis, James; Ayles, Helen

    2014-01-01

    Introduction In many low income countries, the delivery of quality health services is hampered by health system-wide barriers which are often interlinked, however empirical evidence on how to assess the level and scope of these barriers is scarce. A balanced scorecard is a tool that allows for wider analysis of domains that are deemed important in achieving the overall vision of the health system. We present the quantitative results of the 12 months follow-up study applying the balanced scorecard approach in the BHOMA intervention with the aim of demonstrating the utility of the balanced scorecard in evaluating multiple building blocks in a trial setting. Methods The BHOMA is a cluster randomised trial that aims to strengthen the health system in three rural districts in Zambia. The intervention aims to improve clinical care quality by implementing practical tools that establish clear clinical care standards through intensive clinic implementations. This paper reports the findings of the follow-up health facility survey that was conducted after 12 months of intervention implementation. Comparisons were made between those facilities in the intervention and control sites. STATA version 12 was used for analysis. Results The study found significant mean differences between intervention(I) and control (C) sites in the following domains: Training domain (Mean I:C; 87.5.vs 61.1, mean difference 23.3, p = 0.031), adult clinical observation domain (mean I:C; 73.3 vs.58.0, mean difference 10.9, p = 0.02 ) and health information domain (mean I:C; 63.6 vs.56.1, mean difference 6.8, p = 0.01. There was no gender differences in adult service satisfaction. Governance and motivation scores did not differ between control and intervention sites. Conclusion This study demonstrates the utility of the balanced scorecard in assessing multiple elements of the health system. Using system wide approaches and triangulating data collection methods seems to be key to successful

  6. Investigations of the effect of the non-manganese metal in heterometallic-oxido cluster models of the oxygen evolving complex of photosystem II: lanthanides as substitutes for calcium.

    PubMed

    Lin, Po-Heng; Takase, Michael K; Agapie, Theodor

    2015-01-05

    We report the syntheses and electrochemical properties of nine new clusters ([LLnMn(IV)3O4(OAc)3(DMF)n](+) (Ln = La(3+), Ce(3+), Nd(3+), Eu(3+), Gd(3+), Tb(3+), Dy(3+), Yb(3+), and Lu(3+), n = 2 or 3)) supported by a ligand (L(3-)) based on a 1,3,5-triarylbenzene motif appended with alkoxide and pyridine donors. All complexes were obtained by metal substitution of Ca(2+) with lanthanides upon treatment of previously reported LMn3CaO4(OAc)3(THF) with Ln(OTf)3. Structural characterization confirmed that the clusters contain the [LnMn3O4] cubane motif. The effect of the redox-inactive centers on the electronic properties of the Mn3O4 cores was investigated by cyclic voltammetry. A linear correlation between the redox potential of the cluster and the ionic radii or pKa of the lanthanide metal ion was observed. Chemical reduction of the LMn(IV)3GdO4(OAc)3(DMF)2 cluster with decamethylferrocene, resulted in the formation of LGdMn(IV)2Mn(III)O4(OAc)3(DMF)2, a rare example of mixed-valence [MMn3O4] cubane. The lanthanide-coordinated ligands can be substituted with other donors, including water, the biological substrate.

  7. Clustered protocadherins and neuronal diversity.

    PubMed

    Hirayama, Teruyoshi; Yagi, Takeshi

    2013-01-01

    Neuronal diversity is a fundamental requirement for complex neuronal networks and brain function. The clustered protocadherin (Pcdh) family possesses several characteristic features that are important for the molecular basis of neuronal diversity. Clustered Pcdhs are expressed predominantly in the central nervous system, in neurites, growth cones, and synapses. They consist of about 60 isoforms, and their expression is stochastically and combinatorially regulated in individual neurons. The multiple clustered Pcdhs expressed in individual neurons form heteromultimeric protein complexes that exhibit homophilic adhesion properties. Theoretically, the clustered Pcdhs could generate more than 3×10(10) possible variations in each neuron and 12,720 types of cis-tetramers per neuron. The clustered Pcdhs are important for normal neuronal development. The clustered Pcdh genes have also attracted attention as a target for epigenetic regulation.

  8. 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

  9. Native tandem and ion mobility mass spectrometry highlight structural and modular similarities in clustered-regularly-interspaced shot-palindromic-repeats (CRISPR)-associated protein complexes from Escherichia coli and Pseudomonas aeruginosa.

    PubMed

    van Duijn, Esther; Barbu, Ioana M; Barendregt, Arjan; Jore, Matthijs M; Wiedenheft, Blake; Lundgren, Magnus; Westra, Edze R; Brouns, Stan J J; Doudna, Jennifer A; van der Oost, John; Heck, Albert J R

    2012-11-01

    The CRISPR/Cas (clustered regularly interspaced short palindromic repeats/CRISPR-associated genes) immune system of bacteria and archaea provides acquired resistance against viruses and plasmids, by a strategy analogous to RNA-interference. Key components of the defense system are ribonucleoprotein complexes, the composition of which appears highly variable in different CRISPR/Cas subtypes. Previous studies combined mass spectrometry, electron microscopy, and small angle x-ray scattering to demonstrate that the E. coli Cascade complex (405 kDa) and the P. aeruginosa Csy-complex (350 kDa) are similar in that they share a central spiral-shaped hexameric structure, flanked by associating proteins and one CRISPR RNA. Recently, a cryo-electron microscopy structure of Cascade revealed that the CRISPR RNA molecule resides in a groove of the hexameric backbone. For both complexes we here describe the use of native mass spectrometry in combination with ion mobility mass spectrometry to assign a stable core surrounded by more loosely associated modules. Via computational modeling subcomplex structures were proposed that relate to the experimental IMMS data. Despite the absence of obvious sequence homology between several subunits, detailed analysis of sub-complexes strongly suggests analogy between subunits of the two complexes. Probing the specific association of E. coli Cascade/crRNA to its complementary DNA target reveals a conformational change. All together these findings provide relevant new information about the potential assembly process of the two CRISPR-associated complexes.

  10. Light cluster production at NICA

    NASA Astrophysics Data System (ADS)

    Bastian, N.-U.; Batyuk, P.; Blaschke, D.; Danielewicz, P.; Ivanov, Yu. B.; Karpenko, Iu.; Röpke, G.; Rogachevsky, O.; Wolter, H. H.

    2016-08-01

    Light cluster production at the NICA accelerator complex offers unique possibilities to use these states as "rare probes" of in-medium characteristics such as phase space occupation and early flow. In order to explain this statement, in this contribution theoretical considerations from the nuclear statistical equilibrium model and from a quantum statistical model of cluster production are supplemented with a discussion of a transport model for light cluster formation and with results from hydrodynamic simulations combined with the coalescence model.

  11. Hierarchical clustering in minimum spanning trees.

    PubMed

    Yu, Meichen; Hillebrand, Arjan; Tewarie, Prejaas; Meier, Jil; van Dijk, Bob; Van Mieghem, Piet; Stam, Cornelis Jan

    2015-02-01

    The identification of clusters or communities in complex networks is a reappearing problem. The minimum spanning tree (MST), the tree connecting all nodes with minimum total weight, is regarded as an important transport backbone of the original weighted graph. We hypothesize that the clustering of the MST reveals insight in the hierarchical structure of weighted graphs. However, existing theories and algorithms have difficulties to define and identify clusters in trees. Here, we first define clustering in trees and then propose a tree agglomerative hierarchical clustering (TAHC) method for the detection of clusters in MSTs. We then demonstrate that the TAHC method can detect clusters in artificial trees, and also in MSTs of weighted social networks, for which the clusters are in agreement with the previously reported clusters of the original weighted networks. Our results therefore not only indicate that clusters can be found in MSTs, but also that the MSTs contain information about the underlying clusters of the original weighted network.

  12. Hierarchical clustering in minimum spanning trees

    NASA Astrophysics Data System (ADS)

    Yu, Meichen; Hillebrand, Arjan; Tewarie, Prejaas; Meier, Jil; van Dijk, Bob; Van Mieghem, Piet; Stam, Cornelis Jan

    2015-02-01

    The identification of clusters or communities in complex networks is a reappearing problem. The minimum spanning tree (MST), the tree connecting all nodes with minimum total weight, is regarded as an important transport backbone of the original weighted graph. We hypothesize that the clustering of the MST reveals insight in the hierarchical structure of weighted graphs. However, existing theories and algorithms have difficulties to define and identify clusters in trees. Here, we first define clustering in trees and then propose a tree agglomerative hierarchical clustering (TAHC) method for the detection of clusters in MSTs. We then demonstrate that the TAHC method can detect clusters in artificial trees, and also in MSTs of weighted social networks, for which the clusters are in agreement with the previously reported clusters of the original weighted networks. Our results therefore not only indicate that clusters can be found in MSTs, but also that the MSTs contain information about the underlying clusters of the original weighted network.

  13. Large-scale QM/MM calculations of the CaMn4O5 cluster in the S3 state of the oxygen evolving complex of photosystem II. Comparison between water-inserted and no water-inserted structures.

    PubMed

    Shoji, Mitsuo; Isobe, Hiroshi; Nakajima, Takahito; Shigeta, Yasuteru; Suga, Michihiro; Akita, Fusamichi; Shen, Jian-Ren; Yamaguchi, Kizashi

    2017-03-09

    Large-scale QM/MM calculations were performed to elucidate an optimized geometrical structure of a CaMn4O5 cluster with and without water insertion in the S3 state of the oxygen evolving complex (OEC) of photosystem II (PSII). The left (L)-opened structure was found to be stable under the assumption of no hydroxide anion insertion in the S3 state, whereas the right (R)-opened structure became more stable if one water molecule is inserted to the Mn4Ca cluster. The optimized Mna(4)-Mnd(1) distance determined by QM/MM was about 5.0 Å for the S3 structure without an inserted hydroxide anion, but this is elongated by 0.2-0.3 Å after insertion. These computational results are discussed in relation to the possible mechanisms of O-O bond formation in water oxidation by the OEC of PSII.

  14. Cool Cluster Correctly Correlated

    SciTech Connect

    Varganov, Sergey Aleksandrovich

    2005-01-01

    Atomic clusters are unique objects, which occupy an intermediate position between atoms and condensed matter systems. For a long time it was thought that physical and chemical properties of atomic dusters monotonically change with increasing size of the cluster from a single atom to a condensed matter system. However, recently it has become clear that many properties of atomic clusters can change drastically with the size of the clusters. Because physical and chemical properties of clusters can be adjusted simply by changing the cluster's size, different applications of atomic clusters were proposed. One example is the catalytic activity of clusters of specific sizes in different chemical reactions. Another example is a potential application of atomic clusters in microelectronics, where their band gaps can be adjusted by simply changing cluster sizes. In recent years significant advances in experimental techniques allow one to synthesize and study atomic clusters of specified sizes. However, the interpretation of the results is often difficult. The theoretical methods are frequently used to help in interpretation of complex experimental data. Most of the theoretical approaches have been based on empirical or semiempirical methods. These methods allow one to study large and small dusters using the same approximations. However, since empirical and semiempirical methods rely on simple models with many parameters, it is often difficult to estimate the quantitative and even qualitative accuracy of the results. On the other hand, because of significant advances in quantum chemical methods and computer capabilities, it is now possible to do high quality ab-initio calculations not only on systems of few atoms but on clusters of practical interest as well. In addition to accurate results for specific clusters, such methods can be used for benchmarking of different empirical and semiempirical approaches. The atomic clusters studied in this work contain from a few atoms to

  15. Synthesis, characterization, and electronic structures of a series of two-dimensional trimetallic cluster complexes, Ru3(CO)9(mu-SnPh2)3[Pt(PBu(t)3)]x, x = 0-3.

    PubMed

    Adams, Richard D; Captain, Burjor; Hall, Michael B; Trufan, Eszter; Yang, Xinzheng

    2007-10-10

    The triruthenium-tritin cluster complex, Ru3(CO)9(mu-SnPh2)3, 13 was obtained from the reaction of Ru3(CO)12 with Ph3SnH. Compound 13 reacts with Pt(PBut3)2 to yield three new Pt(PBut3) adducts of 13 Ru3(CO)9(mu-SnPh2)3[Pt(PBut3)]x, 14-16 x = 1 - 3 formed by the addition of Pt(PBut3) groups to the Ru-Sn bonds. The new complexes form a novel series of trimetallic complexes having planar arrangements of the metal atoms. The UV-vis absorptions of the four complexes shift progressively to longer wavelengths as the number of platinum atoms is added to the cluster. The electronic structures of these complexes have been investigated in the ground and excited states by density functional theory and time-dependent density functional theory, and this has provided a detailed understanding of the metal-metal bonding and electronic transitions that are responsible for their UV-vis absorption properties. The predicted absorption maximum for the model structures for 13, 14, 15, and 16 at 465, 508, 556, and 585 nm differ only 4-18 nm from the experimental values of 474, 490, 552, and 576 nm. The shift of principal UV-vis absorption can be explained by a lowering of the HOMO-LUMO energy gap due to interactions of the platinum atoms with the HOMO and LUMO of the Ru3Sn3 core.

  16. Structural transitions in clusters.

    PubMed

    Hartke, Bernd

    2002-05-03

    If one adds more particles to a cluster, the energetically optimal structure is neither preserved nor does it change in a continuous fashion. Instead, one finds several cluster size regions where one structural principle dominates almost without exception, and rather narrow boundary regions in-between. The structure of the solid is usually reached only at relatively large sizes, after more than one structural transition. The occurrence of this general phenomenon of size-dependent structural transitions does not seem to depend on the nature of the particles, it is found for atomic, molecular, homogeneous, and heterogeneous clusters alike. Clearly, it is a collective many-body phenomenon which can in principle be calculated but not understood in a fully reductionistic manner. Actual calculations with sufficient accuracy are not feasible today, because of the enormous computational expense, even when unconventional evolutionary algorithms are employed for global geometry optimization. Therefore, simple rules for cluster structures are highly desirable. In fact, we are dealing here not just with the academic quest for linkages between cluster structure and features of the potential energy surface, but structural transitions in clusters are also of immediate relevance for many natural and industrial processes, ranging from crystal growth all the way to nanotechnology. This article provides an exemplary overview of research on this topic, from simple model systems where first qualitative explanations start to be successful, up to more realistic complex systems which are still beyond our understanding.

  17. Quintuplet Cluster

    NASA Technical Reports Server (NTRS)

    1999-01-01

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

  18. 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

  19. An unusual (H(2)O)(20) discrete water cluster in the supramolecular host of a charge transfer platinum(ii) complex: cytotoxicity and DNA cleavage activities.

    PubMed

    Mandal, Sutanuva; Castiñeiras, Alfonso; Mondal, Tapan K; Mondal, Arindam; Chattopadhyay, Dhrubajyoti; Goswami, Sreebrata

    2010-10-28

    The chemical reaction of Pt(II)(L(1))Cl(2) [L(1) = N-4-tolylpyridine-2-aldimine] with a bidentate N,S-donor atom ligand, 2-methylthioaniline, (HL(2)) in alkaline methanolic medium yielded a mixed ligand donor-acceptor complex, [Pt(II)(L(1))(L(2))]Cl, [1]Cl. The complex has been characterized by different spectroscopic and electrochemical techniques. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum (>600 nm). The single-crystal X-ray structure of complex, [1]Cl·3.3H(2)O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of discrete, three dimensional (H(2)O)(20) guest moiety within the reference Pt-complex host lattice. The water assembly showed a unique type of aggregation of a distorted cube encapsulated by hydrogen bonded network of a twelve-water ring. The complex displayed one reversible cathodic response at -0.75 V and two irreversible anodic responses at 0.42 and 0.79 V versus Ag/AgCl reference electrode. The redox processes are characterized by EPR and spectroelectrochemistry. Density-functional theory calculations were employed to confirm the structural features and to support the spectral and redox properties of the complex. The square-planar complex has been found to intercalate DNA. Fluorescence spectroscopy, circular dichroism, cyclic voltammetry, viscosity measurements, together with DNA melting studies have been employed to characterize the binding of [1]Cl with calf thymus DNA. Agarose gel electrophoresis indicates that the complex cleaves supercoiled (SC) pUC19 plasmid DNA to its nicked circular (NC) form via singlet oxygen. As determined by a MTT assay, [1]Cl exhibits significant cytotoxicity with IC(50) value 58 μM.

  20. 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

  1. X-ray Absorption and Emission Spectroscopic Studies of [L2Fe2S2]n Model Complexes: Implications for the Experimental Evaluation of Redox States in Iron–Sulfur Clusters

    PubMed Central

    2016-01-01

    Herein, a systematic study of [L2Fe2S2]n model complexes (where L = bis(benzimidazolato) and n = 2-, 3-, 4-) has been carried out using iron and sulfur K-edge X-ray absorption (XAS) and iron Kβ and valence-to-core X-ray emission spectroscopies (XES). These data are used as a test set to evaluate the relative strengths and weaknesses of X-ray core level spectroscopies in assessing redox changes in iron–sulfur clusters. The results are correlated to density functional theory (DFT) calculations of the spectra in order to further support the quantitative information that can be extracted from the experimental data. It is demonstrated that due to canceling effects of covalency and spin state, the information that can be extracted from Fe Kβ XES mainlines is limited. However, a careful analysis of the Fe K-edge XAS data shows that localized valence vs delocalized valence species may be differentiated on the basis of the pre-edge and K-edge energies. These findings are then applied to existing literature Fe K-edge XAS data on the iron protein, P-cluster, and FeMoco sites of nitrogenase. The ability to assess the extent of delocalization in the iron protein vs the P-cluster is highlighted. In addition, possible charge states for FeMoco on the basis of Fe K-edge XAS data are discussed. This study provides an important reference for future X-ray spectroscopic studies of iron–sulfur clusters. PMID:27097289

  2. Correlation between structure and magnetic spin state of the manganese cluster in the oxygen-evolving complex of photosystem II in the S2 state: determination by X-ray absorption spectroscopy.

    PubMed

    Liang, W; Latimer, M J; Dau, H; Roelofs, T A; Yachandra, V K; Sauer, K; Klein, M P

    1994-04-26

    The structure of the manganese cluster in the S2 state with the g approximately 4 EPR signal (S2-g4 state) generated by 130 K illumination of photosystem II (PSII) membranes prepared from spinach has been investigated by X-ray absorption spectroscopy. The Mn X-ray absorption K-edge spectra of the S2-g4 state not only show a shift of the inflection point to higher energy from the S1 state but also reveal a different edge shape from that of the S2 state with the multiline signal (S2-MLS state). Extended X-ray absorption fine structure (EXAFS) studies of the Mn K-edge show that the structure of the Mn cluster in the S2-g4 state is distinctly different from those in the S2-MLS or S1 states. In the S2-g4 state, the second shell of back-scatters from the Mn absorber is found to contain two Mn-Mn distances of 2.73 and 2.85 A. We interpret this to indicate the presence of two nonequivalent di-mu-oxo-bridged Mn binuclear structures in the Mn cluster of the S2-g4 state. The third shell of the S2-g4 state at about 3.3 A also contains increased heterogeneity. By contrast, very little distance disorder was found to exist in the second shell of the S1 or S2-MLS states. A mechanism is proposed to explain these results in the context of our model for the Mn cluster and the EPR properties of the Mn complex in the S2 state.

  3. Star clusters

    NASA Astrophysics Data System (ADS)

    Labhardt, Lukas; Binggeli, Bruno

    Star clusters are at the heart of astronomy, being key objects for our understanding of stellar evolution and galactic structure. Observations with the Hubble Space Telescope and other modern equipment have revealed fascinating new facts about these galactic building blocks. This book provides two comprehensive and up-to-date, pedagogically designed reviews on star clusters by two well-known experts in the field. Bruce Carney presents our current knowledge of the relative and absolute ages of globular clusters and the chemical history of our Galaxy. Bill Harris addresses globular clusters in external galaxies and their use as tracers of galaxy formation and cosmic distance indicators. The book is written for graduate students as well as professionals in astronomy and astrophysics.

  4. Occupational Clusters.

    ERIC Educational Resources Information Center

    Pottawattamie County School System, Council Bluffs, IA.

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

  5. A complex of Cas proteins 5, 6, and 7 is required for the biogenesis and stability of clustered regularly interspaced short palindromic repeats (crispr)-derived rnas (crrnas) in Haloferax volcanii.

    PubMed

    Brendel, Jutta; Stoll, Britta; Lange, Sita J; Sharma, Kundan; Lenz, Christof; Stachler, Aris-Edda; Maier, Lisa-Katharina; Richter, Hagen; Nickel, Lisa; Schmitz, Ruth A; Randau, Lennart; Allers, Thorsten; Urlaub, Henning; Backofen, Rolf; Marchfelder, Anita

    2014-03-07

    The clustered regularly interspaced short palindromic repeats/CRISPR-associated (CRISPR-Cas) system is a prokaryotic defense mechanism against foreign genetic elements. A plethora of CRISPR-Cas versions exist, with more than 40 different Cas protein families and several different molecular approaches to fight the invading DNA. One of the key players in the system is the CRISPR-derived RNA (crRNA), which directs the invader-degrading Cas protein complex to the invader. The CRISPR-Cas types I and III use the Cas6 protein to generate mature crRNAs. Here, we show that the Cas6 protein is necessary for crRNA production but that additional Cas proteins that form a CRISPR-associated complex for antiviral defense (Cascade)-like complex are needed for crRNA stability in the CRISPR-Cas type I-B system in Haloferax volcanii in vivo. Deletion of the cas6 gene results in the loss of mature crRNAs and interference. However, cells that have the complete cas gene cluster (cas1-8b) removed and are transformed with the cas6 gene are not able to produce and stably maintain mature crRNAs. crRNA production and stability is rescued only if cas5, -6, and -7 are present. Mutational analysis of the cas6 gene reveals three amino acids (His-41, Gly-256, and Gly-258) that are essential for pre-crRNA cleavage, whereas the mutation of two amino acids (Ser-115 and Ser-224) leads to an increase of crRNA amounts. This is the first systematic in vivo analysis of Cas6 protein variants. In addition, we show that the H. volcanii I-B system contains a Cascade-like complex with a Cas7, Cas5, and Cas6 core that protects the crRNA.

  6. Cluster generator

    DOEpatents

    Donchev, Todor I.; Petrov, Ivan G.

    2011-05-31

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

  7. A Complex Insertion Sequence Cluster at a Point of Interaction between the Linear Plasmid SCP1 and the Linear Chromosome of Streptomyces coelicolor A3(2)

    PubMed Central

    Yamasaki, Masayuki; Miyashita, Kiyotaka; Cullum, John; Kinashi, Haruyasu

    2000-01-01

    The giant linear plasmid SCP1 can integrate into the central region of the linear chromosome of Streptomyces coelicolor A3(2). Nucleotide sequence analysis around the target site for SCP1 integration in strain M145 identified a total of five copies of four insertion sequences (ISs) in a 6.5-kb DNA stretch. Three of the four (IS468, IS469, and IS470) are new IS elements, and the other is IS466. All of these elements contain one open reading frame which encodes a transposase-like protein. Two copies of IS468 (IS468A and -B) are tandemly aligned at the left end of the cluster. Following these, IS469 and IS466 are located in a tail-to-tail orientation with 69.3% identity to each other. IS470 is located at the right end of the cluster. The activities of IS466 and IS468 were demonstrated by transposition experiments and sequence comparison of several copies, respectively. PMID:10809688

  8. DICON: interactive visual analysis of multidimensional clusters.

    PubMed

    Cao, Nan; Gotz, David; Sun, Jimeng; Qu, Huamin

    2011-12-01

    Clustering as a fundamental data analysis technique has been widely used in many analytic applications. However, it is often difficult for users to understand and evaluate multidimensional clustering results, especially the quality of clusters and their semantics. For large and complex data, high-level statistical information about the clusters is often needed for users to evaluate cluster quality while a detailed display of multidimensional attributes of the data is necessary to understand the meaning of clusters. In this paper, we introduce DICON, an icon-based cluster visualization that embeds statistical information into a multi-attribute display to facilitate cluster interpretation, evaluation, and comparison. We design a treemap-like icon to represent a multidimensional cluster, and the quality of the cluster can be conveniently evaluated with the embedded statistical information. We further develop a novel layout algorithm which can generate similar icons for similar clusters, making comparisons of clusters easier. User interaction and clutter reduction are integrated into the system to help users more effectively analyze and refine clustering results for large datasets. We demonstrate the power of DICON through a user study and a case study in the healthcare domain. Our evaluation shows the benefits of the technique, especially in support of complex multidimensional cluster analysis.

  9. First principle-based AKMC modelling of the formation and medium-term evolution of point defect and solute-rich clusters in a neutron irradiated complex Fe-CuMnNiSiP alloy representative of reactor pressure vessel steels

    NASA Astrophysics Data System (ADS)

    Ngayam-Happy, R.; Becquart, C. S.; Domain, C.

    2013-09-01

    The formation and medium-term evolution of point defect and solute-rich clusters under neutron irradiation have been modelled in a complex Fe-CuMnNiSiP alloy representative of RPV steels, by means of first principle-based atomistic kinetic Monte Carlo simulations. The results obtained reproduce most features observed in available experimental studies, highlighting the very good agreement between both series. According to simulation, solute-rich clusters form and develop via an induced segregation mechanism on either the vacancy or interstitial clusters, and these point defect clusters are efficiently generated only in cascade debris and not Frenkel pair flux. The results have revealed the existence of two distinct populations of clusters with different characteristic features. Solute-rich clusters in the first group are bound essentially to interstitial clusters and they are enriched in Mn mostly, but also Ni to a lesser extent. Over the low dose regime, their density increases in the alloy as a result of the accumulation of highly stable interstitial clusters. In the second group, the solute-rich clusters are merged with vacancy clusters, and they contain mostly Cu and Si, but also substantial amount of Mn and Ni. The formation of a sub-population of pure solute clusters has been observed, which results from annihilation of the low stable vacancy clusters on sinks. The results indicate finally that the Mn content in clusters is up to 50%, Cu, Si, and Ni sharing the other half in more or less equivalent amounts. This composition has not demonstrated any noticeable modification with increasing dose over irradiation.

  10. The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

    DOE PAGES

    An, Wei; Liu, Ping

    2016-09-07

    When using the TiO2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd7-3D/TiO2(110) at low coverage to Pd7-2D/TiO2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O2 dissociation and CO oxidation via bifunctional synergy.

  11. The complex behavior of the Pd 7 cluster supported on TiO 2 (110) during CO oxidation: adsorbate-driven promoting effect

    SciTech Connect

    An, Wei; Liu, Ping

    2016-09-07

    When using the TiO2(110)-supported Pd7 cluster as a model catalyst, we identified the dynamics of supported metal nanoparticles using density functional theory calculations, at the sub-nanometer scale and under reactive environments. Increasing the CO coverage can induce a structural transformation from Pd7-3D/TiO2(110) at low coverage to Pd7-2D/TiO2(110) at the saturation coverage wherein CO saturation-driven Pd7-2D/TiO2(110) structure displays superior CO oxidation activity at the interfacial sites, which are highly active for catalyzing O2 dissociation and CO oxidation via bifunctional synergy.

  12. Active matter clusters at interfaces.

    NASA Astrophysics Data System (ADS)

    Copenhagen, Katherine; Gopinathan, Ajay

    2016-03-01

    Collective and directed motility or swarming is an emergent phenomenon displayed by many self-organized assemblies of active biological matter such as clusters of embryonic cells during tissue development, cancerous cells during tumor formation and metastasis, colonies of bacteria in a biofilm, or even flocks of birds and schools of fish at the macro-scale. Such clusters typically encounter very heterogeneous environments. What happens when a cluster encounters an interface between two different environments has implications for its function and fate. Here we study this problem by using a mathematical model of a cluster that treats it as a single cohesive unit that moves in two dimensions by exerting a force/torque per unit area whose magnitude depends on the nature of the local environment. We find that low speed (overdamped) clusters encountering an interface with a moderate difference in properties can lead to refraction or even total internal reflection of the cluster. For large speeds (underdamped), where inertia dominates, the clusters show more complex behaviors crossing the interface multiple times and deviating from the predictable refraction and reflection for the low velocity clusters. We then present an extreme limit of the model in the absence of rotational damping where clusters can become stuck spiraling along the interface or move in large circular trajectories after leaving the interface. Our results show a wide range of behaviors that occur when collectively moving active biological matter moves across interfaces and these insights can be used to control motion by patterning environments.

  13. The SMART CLUSTER METHOD - adaptive earthquake cluster analysis and declustering

    NASA Astrophysics Data System (ADS)

    Schaefer, Andreas; Daniell, James; Wenzel, Friedemann

    2016-04-01

    Earthquake declustering is an essential part of almost any statistical analysis of spatial and temporal properties of seismic activity with usual applications comprising of probabilistic seismic hazard assessments (PSHAs) and earthquake prediction methods. The nature of earthquake clusters and subsequent declustering of earthquake catalogues plays a crucial role in determining the magnitude-dependent earthquake return period and its respective spatial variation. Various methods have been developed to address this issue from other researchers. These have differing ranges of complexity ranging from rather simple statistical window methods to complex epidemic models. This study introduces the smart cluster method (SCM), a new methodology to identify earthquake clusters, which uses an adaptive point process for spatio-temporal identification. Hereby, an adaptive search algorithm for data point clusters is adopted. It uses the earthquake density in the spatio-temporal neighbourhood of each event to adjust the search properties. The identified clusters are subsequently analysed to determine directional anisotropy, focussing on a strong correlation along the rupture plane and adjusts its search space with respect to directional properties. In the case of rapid subsequent ruptures like the 1992 Landers sequence or the 2010/2011 Darfield-Christchurch events, an adaptive classification procedure is applied to disassemble subsequent ruptures which may have been grouped into an individual cluster using near-field searches, support vector machines and temporal splitting. The steering parameters of the search behaviour are linked to local earthquake properties like magnitude of completeness, earthquake density and Gutenberg-Richter parameters. The method is capable of identifying and classifying earthquake clusters in space and time. It is tested and validated using earthquake data from California and New Zealand. As a result of the cluster identification process, each event in

  14. Generalized approximate spin projection calculations of effective exchange integrals of the CaMn4O5 cluster in the S1 and S3 states of the oxygen evolving complex of photosystem II.

    PubMed

    Isobe, H; Shoji, M; Yamanaka, S; Mino, H; Umena, Y; Kawakami, K; Kamiya, N; Shen, J-R; Yamaguchi, K

    2014-06-28

    Full geometry optimizations followed by the vibrational analysis were performed for eight spin configurations of the CaMn4O4X(H2O)3Y (X = O, OH; Y = H2O, OH) cluster in the S1 and S3 states of the oxygen evolution complex (OEC) of photosystem II (PSII). The energy gaps among these configurations obtained by vertical, adiabatic and adiabatic plus zero-point-energy (ZPE) correction procedures have been used for computation of the effective exchange integrals (J) in the spin Hamiltonian model. The J values are calculated by the (1) analytical method and the (2) generalized approximate spin projection (AP) method that eliminates the spin contamination errors of UB3LYP solutions. Using J values derived from these methods, exact diagonalization of the spin Hamiltonian matrix was carried out, yielding excitation energies and spin densities of the ground and lower-excited states of the cluster. The obtained results for the right (R)- and left (L)-opened structures in the S1 and S3 states are found to be consistent with available optical and magnetic experimental results. Implications of the computational results are discussed in relation to (a) the necessity of the exact diagonalization for computations of reliable energy levels, (b) magneto-structural correlations in the CaMn4O5 cluster of the OEC of PSII, (c) structural symmetry breaking in the S1 and S3 states, and (d) the right- and left-handed scenarios for the O-O bond formation for water oxidation.

  15. Towards models of the oxygen-evolving complex (OEC) of photosystem II: a Mn4Ca cluster of relevance to low oxidation states of the OEC.

    PubMed

    Koumousi, Evangelia S; Mukherjee, Shreya; Beavers, Christine M; Teat, Simon J; Christou, George; Stamatatos, Theocharis C

    2011-10-21

    Synthetic access has been achieved into high oxidation state Mn/Ca chemistry with the 4 : 1 Mn : Ca stoichiometry of the oxygen-evolving complex (OEC) of plants and cyanobacteria; the anion of (Et(3)NH)(2)[Mn(III)(4)Ca(O(2)CPh)(4)(shi)(4)] has a square pyramidal metal topology and an S = 0 ground state.

  16. High-resolution neutron and X-ray diffraction room-temperature studies of an H-FABP-oleic acid complex: study of the internal water cluster and ligand binding by a transferred multipolar electron-density distribution.

    PubMed

    Howard, E I; Guillot, B; Blakeley, M P; Haertlein, M; Moulin, M; Mitschler, A; Cousido-Siah, A; Fadel, F; Valsecchi, W M; Tomizaki, Takashi; Petrova, T; Claudot, J; Podjarny, A

    2016-03-01

    Crystal diffraction data of heart fatty acid binding protein (H-FABP) in complex with oleic acid were measured at room temperature with high-resolution X-ray and neutron protein crystallography (0.98 and 1.90 Å resolution, respectively). These data provided very detailed information about the cluster of water molecules and the bound oleic acid in the H-FABP large internal cavity. The jointly refined X-ray/neutron structure of H-FABP was complemented by a transferred multipolar electron-density distribution using the parameters of the ELMAMII library. The resulting electron density allowed a precise determination of the electrostatic potential in the fatty acid (FA) binding pocket. Bader's quantum theory of atoms in molecules was then used to study interactions involving the internal water molecules, the FA and the protein. This approach showed H⋯H contacts of the FA with highly conserved hydrophobic residues known to play a role in the stabilization of long-chain FAs in the binding cavity. The determination of water hydrogen (deuterium) positions allowed the analysis of the orientation and electrostatic properties of the water molecules in the very ordered cluster. As a result, a significant alignment of the permanent dipoles of the water molecules with the protein electrostatic field was observed. This can be related to the dielectric properties of hydration layers around proteins, where the shielding of electrostatic interactions depends directly on the rotational degrees of freedom of the water molecules in the interface.

  17. A geological explanation for intraplate earthquake clustering complexity: The zeolite-bearing fault/fracture networks in the Adamello Massif (Southern Italian Alps)

    NASA Astrophysics Data System (ADS)

    Dempsey, E. D.; Holdsworth, R. E.; Imber, J.; Bistacchi, A.; Di Toro, G.

    2014-09-01

    Interconnected networks of faults and veins filled with hydrothermal minerals such as zeolite are widespread in many orogenic terrains. These fractures commonly form at relatively low temperatures (e.g. <200 °C) late in the tectonic history and represent significant phases of fluid flow and mineralisation during exhumation. Zeolite-bearing fractures spatially associated with the Gole Larghe Fault Zone in the Southern Italian Alps are preserved along an interconnected network of variably orientated pre-existing structures. They show evidence of repeated episodes of hydraulic tensile fracturing and small magnitude (total offsets <5 m) shear displacements. We use geological observations and Coulomb stress modelling to propose that repeated seismogenic rupturing of larger offset faults led to local stress transfer and reactivation of widely distributed smaller pre-existing structures in the wall rocks. The differing orientations of the pre-existing features within what is assumed to have been a single regional stress field led to the simultaneous development of reverse, strike-slip and extensional faults. The kinematic diversity and cyclic nature of the hydraulically-assisted deformation suggest that the mineralised fracture systems represent a geological manifestation of intraplate micro-earthquake clusters associated with fluid migration episodes in the upper crust. Our observations highlight the role of crustal fluids and structural reactivation during earthquakes.

  18. A band Lanczos approach for calculation of vibrational coupled cluster response functions: simultaneous calculation of IR and Raman anharmonic spectra for the complex of pyridine and a silver cation.

    PubMed

    Godtliebsen, Ian H; Christiansen, Ove

    2013-07-07

    We describe new methods for the calculation of IR and Raman spectra using vibrational response theory. Using damped linear response functions that incorporate a Lorentzian line-shape function from the outset, it is shown how the calculation of Raman spectra can be carried out through the calculation of a set of vibrational response functions in the same manner as described previously for IR spectra. The necessary set of response functions can be calculated for both vibrational coupled cluster (VCC) and vibrational configuration interaction (VCI) anharmonic vibrational wave-functions. For the efficient and simultaneous calculation of the full set of necessary response functions, a non-hermitian band Lanczos algorithm is implemented for VCC, and a hermitian band Lanczos algorithm is implemented for VCI. It is shown that the simultaneous calculation of several response functions is often advantageous. Sample calculations are presented for pyridine and the complex between pyridine and the silver cation.

  19. H-D exchange in metal carbene complexes: Structure of cluster (μ-H)(μ-OCD3)Os3(CO)9{:C(CD3)NC2H8O}

    NASA Astrophysics Data System (ADS)

    Savkov, Boris; Maksakov, Vladimir; Kuratieva, Natalia

    2015-10-01

    X-ray and spectroscopic data for the new complex (μ-H)(μ-OCH3)Os3(CO)9{:C(CD3)NC2H8O} (2) obtained in the reaction of the (μ-H)(μ-Cl)Os3(CO)9{:C(CH3)NC2H8O} (1) with NaOCD3 in CD3OD solution are reported. It is shown that cluster 1 has the property of CH-acidity inherent of Fisher type carbenes. This had demonstrated using hydrogen deuterium exchange reaction in the presence of a strong base. Bridging chlorine to metoxide ligand substitution takes place during the reaction. The molecular structure of 2 is compared with known analogues.

  20. Large-scale QM/MM calculations of the CaMn4O5 cluster in the oxygen-evolving complex of photosystem II: Comparisons with EXAFS structures

    NASA Astrophysics Data System (ADS)

    Shoji, Mitsuo; Isobe, Hiroshi; Nakajima, Takahito; Yamaguchi, Kizashi

    2016-08-01

    Large-scale QM/MM calculations including hydrogen-bonding networks in the oxygen evolving complex (OEC) of photosystem II (PSII) were performed to elucidate the geometric structures of the CaMn4O5 cluster in the key catalytic states (Si (i = 0-3)). The optimized Mn-Mn, Ca-Mn and Mn-O distances by the large-scale QM/MM starting from the high-resolution XRD structure were consistent with those of the EXAFS experiments in the dark stable S1 state by the Berkeley and Berlin groups. The optimized geometrical parameters for other Si (i = 0, 2, 3) states were also consistent with those of EXAFS, indicating the importance of the large-scale QM/MM calculations for the PSII-OEC.

  1. First insertion of NO into a transition-metal cluster-carbon bond: regioselective formation, structure, and reactions of the first alkanenitrile oxide complexes

    SciTech Connect

    Goldhaber, A.; Vollhardt, K.P.C.; Walborsky, E.C.; Wolfgruber, M.

    1986-02-05

    The chemistry of NO in the presence of transition metals is receiving considerable current attention because of its role in air pollution, its potential in organic synthesis by carbon-nitrogen bond formation, and an increasing interest in its basic features. The nitrosyl cation has been reacted with many mono and polynuclear metal systems, leading mainly to substitution and reduction. Insertion into alkyl and aryl metal bonds in mono-metallic complexes is documented. The unprecedented title reaction and some preliminary chemistry of the products are reported here. 27 references, 1 figure.

  2. A Robust Open Framework Formed by Decavanadate Clusters and Copper(II) Complexes of Macrocyclic Polyamines: Permanent Microporosity and Catalytic Oxidation of Cycloalkanes.

    PubMed

    Martín-Caballero, Jagoba; San José Wéry, Ana; Reinoso, Santiago; Artetxe, Beñat; San Felices, Leire; El Bakkali, Bouchra; Trautwein, Guido; Alcañiz-Monge, Juan; Vilas, José Luis; Gutiérrez-Zorrilla, Juan M

    2016-05-16

    The first decavanadate-based microporous hybrid, namely, [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1, cyclam = 1,4,8,11-tetraazacyclotetradecane) was prepared by reaction of (VO3)(-) anions and {Cu(cyclam)}(2+) complexes in NaCl (aq) at pH 4.6-4.7 and characterized by elemental analyses, thermogravimetry, and X-ray diffraction (powder, single-crystal) techniques. Compound 1 exhibits a POMOF-like supramolecular open-framework built of covalent decavanadate/metalorganic layers with square-like voids, the stacking of which is aided by interlamellar cementing complexes and generates water-filled channels with approximate cross sections of 10.4 × 8.8 Å(2). The framework is robust enough to remain virtually unaltered upon thermal evacuation of all water molecules of hydration, as demonstrated through single-crystal X-ray diffraction studies on the anhydrous phase 1a. This permanent microporosity renders interesting functionality to 1, such as selective adsorption of CO2 over N2 and remarkable activity as heterogeneous catalyst toward the H2O2-based oxidation of the highly-stable, tricyclic alkane adamantane.

  3. Cluster bulleticity

    NASA Astrophysics Data System (ADS)

    Massey, Richard; Kitching, Thomas; Nagai, Daisuke

    2011-05-01

    The unique properties of dark matter are revealed during collisions between clusters of galaxies, such as the bullet cluster (1E 0657-56) and baby bullet (MACS J0025-12). These systems provide evidence for an additional, invisible mass in the separation between the distributions of their total mass, measured via gravitational lensing, and their ordinary 'baryonic' matter, measured via its X-ray emission. Unfortunately, the information available from these systems is limited by their rarity. Constraints on the properties of dark matter, such as its interaction cross-section, are therefore restricted by uncertainties in the individual systems' impact velocity, impact parameter and orientation with respect to the line of sight. Here we develop a complementary, statistical measurement in which every piece of substructure falling into every massive cluster is treated as a bullet. We define 'bulleticity' as the mean separation between dark matter and ordinary matter, and we measure the signal in hydrodynamical simulations. The phase space of substructure orbits also exhibits symmetries that provide an equivalent control test. Any detection of bulleticity in real data would indicate a difference in the interaction cross-sections of baryonic and dark matter that may rule out hypotheses of non-particulate dark matter that are otherwise able to model individual systems. A subsequent measurement of bulleticity could constrain the dark matter cross-section. Even with conservative estimates, the existing Hubble Space Telescope archive should yield an independent constraint tighter than that from the bullet cluster. This technique is then trivially extendable to and benefits enormously from larger, future surveys.

  4. Active matter clusters at interfaces

    NASA Astrophysics Data System (ADS)

    Copenhagen, Katherine; Gopinathan, Ajay

    Collective and directed motility or swarming is an emergent phenomenon displayed by many self-organized assemblies of active biological matter such as clusters of embryonic cells during tissue development and flocks of birds. Such clusters typically encounter very heterogeneous environments. What happens when a cluster encounters an interface between two different environments has implications for its function and fate. Here we study this problem by using a mathematical model of a cluster that treats it as a single cohesive unit whose movement depends on the nature of the local environment. We find that low speed clusters which exert forces but no active torques, encountering an interface with a moderate difference in properties can lead to refraction or even total internal reflection of the cluster. For large speeds and clusters with active torques, they show more complex behaviors crossing the interface multiple times, becoming trapped at the interface and deviating from the predictable refraction and reflection of the low velocity clusters. Our results show a wide range of behaviors that occur when collectively moving active biological matter moves across interfaces and these insights can be used to control motion by patterning environments.

  5. Full geometry optimizations of the CaMn4O4 model cluster for the oxygen evolving complex of photosystem II

    NASA Astrophysics Data System (ADS)

    Shoji, Mitsuo; Isobe, Hiroshi; Nakajima, Takahito; Yamaguchi, Kizashi

    2015-11-01

    Full geometry optimizations of ([CaMn4O4(CH3COO)8(py)(CH3COOH)2], (py: pyridine) (1)) were performed at the UB3LYP theoretical level. 1 is a theoretical model for the synthetic model ([CaMn4O4(ButCOO)8(py)(ButCOOH)2], (But: t-butyl) (2)) which closely mimicks the native oxygen evolving complex (OEC) in photosystem II. It was shown that the X-ray structure of 2 was well reproduced by 1 in the (Mn1(III), Mn2(IV), Mn3(IV), Mn4(III)) valence state with the unprotonated O5 (O5 = O2-), and two different valence states were obtained in the one-electron oxidized state. Importance of the Jahn-Teller effect of the Mn(III) site for the structural deformations was presented.

  6. Toward Parallel Document Clustering

    SciTech Connect

    Mogill, Jace A.; Haglin, David J.

    2011-09-01

    A key challenge to automated clustering of documents in large text corpora is the high cost of comparing documents in a multimillion dimensional document space. The Anchors Hierarchy is a fast data structure and algorithm for localizing data based on a triangle inequality obeying distance metric, the algorithm strives to minimize the number of distance calculations needed to cluster the documents into “anchors” around reference documents called “pivots”. We extend the original algorithm to increase the amount of available parallelism and consider two implementations: a complex data structure which affords efficient searching, and a simple data structure which requires repeated sorting. The sorting implementation is integrated with a text corpora “Bag of Words” program and initial performance results of end-to-end a document processing workflow are reported.

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

    PubMed

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

    2013-04-22

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

  8. High-resolution neutron and X-ray diffraction room-temperature studies of an H-FABP–oleic acid complex: study of the internal water cluster and ligand binding by a transferred multipolar electron-density distribution

    PubMed Central

    Howard, E. I.; Guillot, B.; Blakeley, M. P.; Haertlein, M.; Moulin, M.; Mitschler, A.; Cousido-Siah, A.; Fadel, F.; Valsecchi, W. M.; Tomizaki, Takashi; Petrova, T.; Claudot, J.; Podjarny, A.

    2016-01-01

    Crystal diffraction data of heart fatty acid binding protein (H-FABP) in complex with oleic acid were measured at room temperature with high-resolution X-ray and neutron protein crystallography (0.98 and 1.90 Å resolution, respectively). These data provided very detailed information about the cluster of water molecules and the bound oleic acid in the H-FABP large internal cavity. The jointly refined X-ray/neutron structure of H-FABP was complemented by a transferred multipolar electron-density distribution using the parameters of the ELMAMII library. The resulting electron density allowed a precise determination of the electrostatic potential in the fatty acid (FA) binding pocket. Bader’s quantum theory of atoms in molecules was then used to study interactions involving the internal water molecules, the FA and the protein. This approach showed H⋯H contacts of the FA with highly conserved hydrophobic residues known to play a role in the stabilization of long-chain FAs in the binding cavity. The determination of water hydrogen (deuterium) positions allowed the analysis of the orientation and electrostatic properties of the water molecules in the very ordered cluster. As a result, a significant alignment of the permanent dipoles of the water molecules with the protein electrostatic field was observed. This can be related to the dielectric properties of hydration layers around proteins, where the shielding of electrostatic interactions depends directly on the rotational degrees of freedom of the water molecules in the interface. PMID:27006775

  9. Chemical evolution of star clusters.

    PubMed

    van Loon, Jacco Th

    2010-02-28

    I discuss the chemical evolution of star clusters, with emphasis on old Galactic globular clusters (GCs), in relation to their formation histories. GCs are clearly formed in a complex fashion, under markedly different conditions from any younger clusters presently known. Those special conditions must be linked to the early formation epoch of the Galaxy and must not have occurred since. While a link to the formation of GCs in dwarf galaxies has been suggested, present-day dwarf galaxies are not representative of the gravitational potential wells within which the GCs formed. Instead, a formation deep within the proto-Galaxy or within dark-matter mini-haloes might be favoured. Not all GCs may have formed and evolved similarly. In particular, we may need to distinguish Galactic Halo from Galactic Bulge clusters.

  10. Architecture of Eph receptor clusters

    SciTech Connect

    Himanen, Juha P.; Yermekbayeva, Laila; Janes, Peter W.; Walker, John R.; Xu, Kai; Atapattu, Lakmali; Rajashankar, Kanagalaghatta R.; Mensinga, Anneloes; Lackmann, Martin; Nikolov, Dimitar B.; Dhe-Paganon, Sirano

    2010-10-04

    Eph receptor tyrosine kinases and their ephrin ligands regulate cell navigation during normal and oncogenic development. Signaling of Ephs is initiated in a multistep process leading to the assembly of higher-order signaling clusters that set off bidirectional signaling in interacting cells. However, the structural and mechanistic details of this assembly remained undefined. Here we present high-resolution structures of the complete EphA2 ectodomain and complexes with ephrin-A1 and A5 as the base unit of an Eph cluster. The structures reveal an elongated architecture with novel Eph/Eph interactions, both within and outside of the Eph ligand-binding domain, that suggest the molecular mechanism underlying Eph/ephrin clustering. Structure-function analysis, by using site-directed mutagenesis and cell-based signaling assays, confirms the importance of the identified oligomerization interfaces for Eph clustering.

  11. The [Sn(9)Pt(2)(PPh(3))](2)(-) and [Sn(9)Ni(2)(CO)](3)(-) complexes: two markedly different Sn(9)M(2)L transition metal zintl ion clusters and their dynamic behavior.

    PubMed

    Kesanli, Banu; Fettinger, James; Gardner, Donna R; Eichhorn, Bryan

    2002-05-01

    [Sn(9)Pt(2)(PPh(3))](2)(-) (2) was prepared from Pt(PPh(3))(4), K(4)Sn(9), and 2,2,2-cryptand in en/toluene solvent mixtures. The [K(2,2,2-cryptand)](+) salt is very air and moisture sensitive and has been characterized by ESI-MS, variable-temperature (119)Sn, (31)P, and (195)Pt NMR and single-crystal X-ray diffraction studies. The structure of 2 comprises an elongated tricapped Sn(9) trigonal prism with a capping PtPPh(3), an interstitial Pt atom, a hypercloso electron count (10 vertex, 20 electron) and C(3)(v)() point symmetry. Hydrogenation trapping experiments and deuterium labeling studies showed that the formation of 2 involves a double C-H activation of solvent molecules (en or DMSO) with the elimination of H(2) gas. The ESI-MS analysis of 2 showed the K[Sn(9)Pt(2)(PPh(3))](1)(-) parent ion, an oxidized [Sn(9)Pt(2)(PPh(3))](1)(-) ion, and the protonated binary cluster anion [HSn(9)Pt(2)](1)(-). 2 is highly fluxional in solution giving rise to a single time-averaged (119)Sn NMR signal for all nine Sn atoms but the Pt atoms remain distinct. The exchange is intramolecular and is consistent with a rigid, linear Pt-Pt-PPh(3) rod embedded in a liquidlike Sn(9) matrix. [Sn(9)Ni(2)(CO)](3)(-) (3) was prepared from Ni(CO)(2)(PPh(3))(2), K(4)Sn(9), and 2,2,2-cryptand in en/toluene solvent mixtures. The [K(2,2,2-cryptand)](+) salt is very air and moisture sensitive, is paramagnetic, and has been characterized by ESI-MS, EPR, and single-crystal X-ray diffraction. Complex 3 is a 10-vertex 21-electron polyhedron, a slightly distorted closo-Sn(9)Ni cluster with an additional interstitial Ni atom and overall C(4)(v)() point symmetry. The EPR spectrum showed a five-line pattern due to 4.8-G hyperfine interactions involving all nine tin atoms. The ESI-MS analysis showed weak signals for the potassium complex [K(2)Sn(9)Ni(2)(CO)](1-) and the ligand-free binary ions [K(2)Sn(9)Ni(2)](1)(-), [KSn(9)Ni(2)](1)(-), and [HSn(9)Ni(2)](1)(-).

  12. Clustering Millions of Faces by Identity.

    PubMed

    Otto, Charles; Wang, Dayong; Jain, Anil

    2017-03-07

    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 (13K faces of 5; 749 individuals), which drops to 0:27 on the largest dataset considered (13K 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.

  13. Contribution of globular clusters to halos

    NASA Astrophysics Data System (ADS)

    Bragaglia, Angela

    2017-03-01

    The contribution of massive star clusters to their hosting halo dramatically depends on their formation mechanism and their early evolution. Massive globular clusters in the Milky Way (and in other galaxies) have been shown to display peculiar chemical patterns (light-elements correlations and anti-correlations) indicative of a complex star formation, confirmed by photometric evidence (spread or split sequences). I use these chemical signatures to try to understand what is the fraction of halo stars originally born in globular clusters.

  14. Expulsion of Dust from Young Stellar Clusters

    NASA Astrophysics Data System (ADS)

    Grosbøl, P.; Dottori, H.

    2013-03-01

    Young stellar clusters were identified on deep near-infrared images of 6 nearby, grand-design spirals observed with HAWK-I/VLT. A 90% completeness was reached for cluster complexes with M K = -11.5m (corresponding to masses around 104 M⊙) while the linear resolution was around 40 pc. The distribution of clusters in the (H-K)-(J-H) diagrams revealed two groups of clusters. Comparing with Starburst99 model tracks, the groups could be interpreted as one old population of clusters with low extinction and one consisting of young clusters with visual extinction as high as AV = 7m. The clear separation between the two groups suggests a rapid expulsion of dust from the young clusters.

  15. Astrophysics of galaxy clusters

    NASA Astrophysics Data System (ADS)

    Ettori, Stefano

    2016-07-01

    As the nodes of the cosmic web, clusters of galaxies trace the large-scale distribution of matter in the Universe. They are thus privileged sites in which to investigate the complex physics of structure formation. However, the complete story of how these structures grow, and how they dissipate the gravitational and non-thermal components of their energy budget over cosmic time, is still beyond our grasp. Most of the baryons gravitationally bound to the cluster's halo is in the form of a diffuse, hot, metal-enriched plasma that radiates primarily in the X-ray band. X-ray observations of the evolving cluster population provide a unique opportunity to address such fundamental open questions as: How do hot diffuse baryons accrete and dynamically evolve in dark matter potentials? How and when was the energy that we observe in the ICM generated and distributed? Where and when are heavy elements produced and how are they circulated? We will present the ongoing activities to define the strategy on how an X-ray observatory with large collecting area and an unprecedented combination of high spectral and angular resolution, such as Athena, can address these questions.

  16. Probing the topography of the photosystem II oxygen evolving complex: PsbO is required for efficient calcium protection of the manganese cluster against dark-inhibition by an artificial reductant.

    PubMed

    Popelkova, Hana; Boswell, Nicholas; Yocum, Charles

    2011-12-01

    The photosystem II (PSII) manganese-stabilizing protein (PsbO) is known to be the essential PSII extrinsic subunit for stabilization and retention of the Mn and Cl(-) cofactors in the oxygen evolving complex (OEC) of PSII, but its function relative to Ca(2+) is less clear. To obtain a better insight into the relationship, if any, between PsbO and Ca(2+) binding in the OEC, samples with altered PsbO-PSII binding properties were probed for their potential to promote the ability of Ca(2+) to protect the Mn cluster against dark-inhibition by an exogenous artificial reductant, N,N-dimethylhydroxylamine. In the absence of the PsbP and PsbQ extrinsic subunits, Ca(2+) and its surrogates (Sr(2+), Cd(2+)) shield Mn atoms from inhibitory reduction (Kuntzleman et al., Phys Chem Chem Phys 6:4897, 2004). The results presented here show that PsbO exhibits a positive effect on Ca(2+) binding in the OEC by facilitating the ability of the metal to prevent inhibition of activity by the reductant. The data presented here suggest that PsbO may have a role in the formation of the OEC-associated Ca(2+) binding site by promoting the equilibrium between bound and free Ca(2+) that favors the bound metal.

  17. Cluster headache

    PubMed Central

    Leroux, Elizabeth; Ducros, Anne

    2008-01-01

    Cluster headache (CH) is a primary headache disease characterized by recurrent short-lasting attacks (15 to 180 minutes) of excruciating unilateral periorbital pain accompanied by ipsilateral autonomic signs (lacrimation, nasal congestion, ptosis, miosis, lid edema, redness of the eye). It affects young adults, predominantly males. Prevalence is estimated at 0.5–1.0/1,000. CH has a circannual and circadian periodicity, attacks being clustered (hence the name) in bouts that can occur during specific months of the year. Alcohol is the only dietary trigger of CH, strong odors (mainly solvents and cigarette smoke) and napping may also trigger CH attacks. During bouts, attacks may happen at precise hours, especially during the night. During the attacks, patients tend to be restless. CH may be episodic or chronic, depending on the presence of remission periods. CH is associated with trigeminovascular activation and neuroendocrine and vegetative disturbances, however, the precise cautive mechanisms remain unknown. Involvement of the hypothalamus (a structure regulating endocrine function and sleep-wake rhythms) has been confirmed, explaining, at least in part, the cyclic aspects of CH. The disease is familial in about 10% of cases. Genetic factors play a role in CH susceptibility, and a causative role has been suggested for the hypocretin receptor gene. Diagnosis is clinical. Differential diagnoses include other primary headache diseases such as migraine, paroxysmal hemicrania and SUNCT syndrome. At present, there is no curative treatment. There are efficient treatments to shorten the painful attacks (acute treatments) and to reduce the number of daily attacks (prophylactic treatments). Acute treatment is based on subcutaneous administration of sumatriptan and high-flow oxygen. Verapamil, lithium, methysergide, prednisone, greater occipital nerve blocks and topiramate may be used for prophylaxis. In refractory cases, deep-brain stimulation of the hypothalamus and

  18. Oxygen atom transfer reactions from dioxygen to phosphines via a bridging sulfur dioxide in a trinuclear cluster complex of rhenium, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)].

    PubMed

    Saito, Taro; Sunaga, Tomoaki; Sakai, Nobuaki; Nakamura, Yoichi; Yamamoto, Saori; Iriuchijima, Daisuke; Yoza, Kenji

    2005-06-13

    A trinuclear rhenium sulfide cluster complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(3)Cl(6)(PMe(2)Ph)(3)], synthesized from Re(3)S(7)Cl(7), dimethylphenylphosphine, and [(Ph(3)P)(2)N]Cl is readily converted to a bridging SO(2) complex, [(Ph(3)P)(2)N][Re(3)(mu(3)-S)(mu-S)(2)(mu-SO(2))Cl(6)(PMe(2)Ph)(3)], by reaction with O(2). The oxygen atoms on the SO(2) ligand react with phosphines or phosphites to form phosphine oxides or phosphates, and the original cluster complex is recovered. The reaction course has been monitored by (31)P NMR as well as by UV-vis spectroscopy. The catalytic oxygenation of PMePh(2) in the presence of the SO(2) complex shows that turnovers are 8 per hour at 23 degrees C in CDCl(3). The X-ray structures of the cluster complexes are described.

  19. SCIMES: Spectral Clustering for Interstellar Molecular Emission Segmentation

    NASA Astrophysics Data System (ADS)

    Colombo, Dario; Rosolowsky, Erik; Ginsburg, Adam; Duarte-Cabral, Ana; Hughes, Annie

    2016-09-01

    SCIMES identifies relevant molecular gas structures within dendrograms of emission using the spectral clustering paradigm. It is useful for decomposing objects in complex environments imaged at high resolution.

  20. Splitting Methods for Convex Clustering

    PubMed Central

    Chi, Eric C.; Lange, Kenneth

    2016-01-01

    Clustering is a fundamental problem in many scientific applications. Standard methods such as k-means, Gaussian mixture models, and hierarchical clustering, however, are beset by local minima, which are sometimes drastically suboptimal. Recently introduced convex relaxations of k-means and hierarchical clustering shrink cluster centroids toward one another and ensure a unique global minimizer. In this work we present two splitting methods for solving the convex clustering problem. The first is an instance of the alternating direction method of multipliers (ADMM); the second is an instance of the alternating minimization algorithm (AMA). In contrast to previously considered algorithms, our ADMM and AMA formulations provide simple and unified frameworks for solving the convex clustering problem under the previously studied norms and open the door to potentially novel norms. We demonstrate the performance of our algorithm on both simulated and real data examples. While the differences between the two algorithms appear to be minor on the surface, complexity analysis and numerical experiments show AMA to be significantly more efficient. This article has supplemental materials available online. PMID:27087770

  1. Uranyl peroxide closed clusters containing topological squares

    SciTech Connect

    Unruh, Daniel K.; Burtner, Alicia; Pressprich, Laura; Sigmon, Ginger E.; Burns, Peter C

    2010-01-01

    Four self-assembling clusters of uranyl peroxide polyhedra have been formed in alkaline aqueous solutions and structurally characterized. These clusters consist of 28, 30, 36 and 44 uranyl polyhedra and exhibit complex new topologies. Each has a structure that contains topological squares, pentagons and hexagons. Analysis of possible topologies within boundary constraints indicates a tendency for adoption of higher symmetry topologies in these cases. Small angle X-ray scattering data demonstrated that crystals of one of these clusters can be dissolved in ultrapure water and that the clusters remain intact for at least several days.

  2. Star Clusters in the Magellanic Clouds

    NASA Astrophysics Data System (ADS)

    Gallagher, J. S., III

    2014-09-01

    The Magellanic Clouds (MC) are prime locations for studies of star clusters covering a full range in age and mass. This contribution briefly reviews selected properties of Magellanic star clusters, by focusing first on young systems that show evidence for hierarchical star formation. The structures and chemical abundance patterns of older intermediate age star clusters in the Small Magellanic Cloud (SMC) are a second topic. These suggest a complex history has affected the chemical enrichment in the SMC and that low tidal stresses in the SMC foster star cluster survival.

  3. Dimensionality Reduction Particle Swarm Algorithm for High Dimensional Clustering

    SciTech Connect

    Cui, Xiaohui; ST Charles, Jesse Lee; Potok, Thomas E; Beaver, Justin M

    2008-01-01

    The Particle Swarm Optimization (PSO) clustering algorithm can generate more compact clustering results than the traditional K-means clustering algorithm. However, when clustering high dimensional datasets, the PSO clustering algorithm is notoriously slow because its computation cost increases exponentially with the size of the dataset dimension. Dimensionality reduction techniques offer solutions that both significantly improve the computation time, and yield reasonably accurate clustering results in high dimensional data analysis. In this paper, we introduce research that combines different dimensionality reduction techniques with the PSO clustering algorithm in order to reduce the complexity of high dimensional datasets and speed up the PSO clustering process. We report significant improvements in total runtime. Moreover, the clustering accuracy of the dimensionality reduction PSO clustering algorithm is comparable to the one that uses full dimension space.

  4. The longitudinal development of clusters in French.

    PubMed

    Demuth, Katherine; McCullough, Elizabeth

    2009-03-01

    Studies of English and German find that children tend to acquire word-final consonant clusters before word-initial consonant clusters. This order of acquisition is generally attributed to articulatory, frequency and/or morphological factors. This contrasts with recent experimental findings from French, where two-year-olds were better at producing word-initial than word-final clusters (Demuth & Kehoe, 2006). The purpose of the present study was to examine French-speaking children's longitudinal acquisition of clusters to determine if these results replicate developmentally. Analysis of spontaneous speech productions from two French-speaking children between one and three years confirmed the earlier acquisition of initial clusters, even when sonority factors were controlled. The findings suggest that French-speaking children acquire complexity at the beginnings of words before complexity appears word-finally. The role of frequency, morphological, structural and input factors is discussed.

  5. Synthesis and structure of a water-soluble hexanuclear silver(I) nicotinate cluster comprised of a "cyclohexane-chair"-type of framework, showing effective antibacterial and antifungal activities: use of "sparse matrix" techniques for growing crystals of water-soluble inorganic complexes.

    PubMed

    Tsyba, Irina; Mui, Becky Bun-Kit; Bau, Robert; Noguchi, Ryusuke; Nomiya, Kenji

    2003-12-01

    The synthesis of a water-soluble anionic silver 2-mercaptonicotinate complex having effective antibacterial and antifungal properties is described. Its structure has been confirmed to be a hexameric cluster by an X-ray diffraction analysis of a mixed Na(+)/Tris(+) salt (Tris(+) = tris(hydroxymethyl)methylammonium cation). The [Ag(mna)](6)(6-) cluster has a Ag(6)S(6) core and an overall shape of twisted hexagonal cylinder with six sulfur atoms and six silver atoms alternating on a puckered drum-like surface. Each Ag atom is trigonally coordinated by one N and two S ligands. The overall [Ag(mna)](6)(6-).4Na(+).2[(HOCH(2))(3)CNH(3)](+).10H(2)O complex has a layered appearance in the crystal packing diagram, with a [Ag(mna)](6)(-) cluster layer alternating with a solvent layer consisting of sodium atoms, Tris buffer cations, and water molecules. The structure is almost identical to that of a neutral [Ag(Hmna)](6) complex reported earlier. The neutral and charged complexes are both known to possess antimicrobial activities, and some biological properties of these and related compounds are briefly discussed in this paper.

  6. 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

  7. Kinematics and dynamics of the MKW/AWM poor clusters

    NASA Technical Reports Server (NTRS)

    Beers, Timothy C.; Kriessler, Jeffrey R.; Bird, Christina M.; Huchra, John P.

    1995-01-01

    We report 472 new redshifts for 416 galaxies in the regions of the 23 poor clusters of galaxies originally identified by Morgan, Kayser, and White (MKW), and Albert, White, and Morgan (AWM). Eighteen of the poor clusters now have 10 or more available redshifts within 1.5/h Mpc of the central galaxy; 11 clusters have at least 20 available redshifts. Based on the 21 clusters for which we have sufficient velocity information, the median velocity scale is 336 km/s, a factor of 2 smaller than found for rich clusters. Several of the poor clusters exhibit complex velocity distributions due to the presence of nearby clumps of galaxies. We check on the velocity of the dominant galaxy in each poor cluster relative to the remaining cluster members. Significantly high relative velocities of the dominant galaxy are found in only 4 of 21 poor clusters, 3 of which we suspect are due to contamination of the parent velocity distribution. Several statistical tests indicate that the D/cD galaxies are at the kinematic centers of the parent poor cluster velocity distributions. Mass-to-light ratios for 13 of the 15 poor clusters for which we have the required data are in the range 50 less than or = M/L(sub B(0)) less than or = 200 solar mass/solar luminosity. The complex nature of the regions surrounding many of the poor clusters suggests that these groupings may represent an early epoch of cluster formation. For example, the poor clusters MKW7 and MKWS are shown to be gravitationally bound and likely to merge to form a richer cluster within the next several Gyrs. Eight of the nine other poor clusters for which simple two-body dynamical models can be carried out are consistent with being bound to other clumps in their vicinity. Additional complex systems with more than two gravitationally bound clumps are observed among the poor clusters.

  8. Iterative Discovery of Multiple AlternativeClustering Views.

    PubMed

    Donglin Niu; Dy, Jennifer G; Jordan, Michael I

    2014-07-01

    Complex data can be grouped and interpreted in many different ways. Most existing clustering algorithms, however, only find one clustering solution, and provide little guidance to data analysts who may not be satisfied with that single clustering and may wish to explore alternatives. We introduce a novel approach that provides several clustering solutions to the user for the purposes of exploratory data analysis. Our approach additionally captures the notion that alternative clusterings may reside in different subspaces (or views). We present an algorithm that simultaneously finds these subspaces and the corresponding clusterings. The algorithm is based on an optimization procedure that incorporates terms for cluster quality and novelty relative to previously discovered clustering solutions. We present a range of experiments that compare our approach to alternatives and explore the connections between simultaneous and iterative modes of discovery of multiple clusterings.

  9. 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

  10. INTERRUPTED STELLAR ENCOUNTERS IN STAR CLUSTERS

    SciTech Connect

    Geller, Aaron M.; Leigh, Nathan W. C. E-mail: nleigh@amnh.org

    2015-07-20

    Strong encounters between single stars and binaries play a pivotal role in the evolution of star clusters. Such encounters can also dramatically modify the orbital parameters of binaries, exchange partners in and out of binaries, and are a primary contributor to the rate of physical stellar collisions in star clusters. Often, these encounters are studied under the approximation that they happen quickly enough and within a small enough volume to be considered isolated from the rest of the cluster. In this paper, we study the validity of this assumption through the analysis of a large grid of single–binary and binary–binary scattering experiments. For each encounter we evaluate the encounter duration, and compare this with the expected time until another single or binary star will join the encounter. We find that for lower-mass clusters, similar to typical open clusters in our Galaxy, the percent of encounters that will be “interrupted” by an interloping star or binary may be 20%–40% (or higher) in the core, though for typical globular clusters we expect ≲1% of encounters to be interrupted. Thus, the assumption that strong encounters occur in relative isolation breaks down for certain clusters. Instead, many strong encounters develop into more complex “mini-clusters,” which must be accounted for in studying, for example, the internal dynamics of star clusters, and the physical stellar collision rate.

  11. Triangular oxalate clusters [W(3)(mu(3)-S)(mu(2)-S(2))(3)(C(2)O(4))(3)](2)(-) as building blocks for coordination polymers and nanosized complexes.

    PubMed

    Sokolov, Maxim N; Gushchin, Artem L; Kovalenko, Konstantin A; Peresypkina, Eugenia V; Virovets, Alexander V; Sanchiz, Joaquin; Fedin, Vladimir P

    2007-03-19

    The reaction of aqueous [W3S7(C2O4)3](2-) with Ln(3+) and Th(4+) in a 1:1 molar ratio leads to oxalate-bridged heteropolynuclear molecular complexes and coordination polymers. La(3+) and Ce(3+) give a layered structure with big (about 1.8 nm) honeycomb pores which are filled with water molecules and lanthanide ions, in {[Ln(H2O)6]3[W3S7(C2O4)3]4}Br x xH2O (Ia and Ib). The smaller Pr(3+), Nd(3+), Sm(3+), Eu(3+), and Gd(3+) ions give discrete nanomolecules [(W3S7(C2O4)3Ln(H2O)5)2(mu-C2O4)] (with a separation of about 3.2 nm between the most distant parts of the molecule), which are further united into zigzag chains by specific S2...Br- contacts to achieve the overall stoichiometry K[(W3S7(C2O4)3Ln(H2O)5)2(mu-C2O4)]Br.xH2O (IIa-IId). Th(4+) gives K2[(W3S7(C2O4)3)4Th2(OH)2(H2O)10] x 14.33H2O (III) with a nanosized discrete anion (with a separation of about 2.7 nm between the most distant parts of the molecule), in which two thorium atoms are bound via two hydroxide groups into the Th2(OH)2(6+) unit, and each Th is further coordinated by five water molecules and two monodentate [W3S7(C2O4)](2-) cluster ligands. All compounds were characterized by X-ray structure analysis and IR spectroscopy. Magnetic susceptibility measurements in the temperature range of 2-300 K show weak antiferromagnetic interactions between two lanthanides atoms for compounds IIa, IIb, and IId. The thermal decomposition of Ia, Ib, and IIb was studied by thermogravimetry.

  12. A Bridging [4Fe-4S] Cluster and Nucleotide Binding Are Essential for Function of the Cfd1-Nbp35 Complex as a Scaffold in Iron-Sulfur Protein Maturation*

    PubMed Central

    Netz, Daili J. A.; Pierik, Antonio J.; Stümpfig, Martin; Bill, Eckhard; Sharma, Anil K.; Pallesen, Leif J.; Walden, William E.; Lill, Roland

    2012-01-01

    The essential P-loop NTPases Cfd1 and Nbp35 of the cytosolic iron-sulfur (Fe-S) protein assembly machinery perform a scaffold function for Fe-S cluster synthesis. Both proteins contain a nucleotide binding motif of unknown function and a C-terminal motif with four conserved cysteine residues. The latter motif defines the Mrp/Nbp35 subclass of P-loop NTPases and is suspected to be involved in transient Fe-S cluster binding. To elucidate the function of these two motifs, we first created cysteine mutant proteins of Cfd1 and Nbp35 and investigated the consequences of these mutations by genetic, cell biological, biochemical, and spectroscopic approaches. The two central cysteine residues (CPXC) of the C-terminal motif were found to be crucial for cell viability, protein function, coordination of a labile [4Fe-4S] cluster, and Cfd1-Nbp35 hetero-tetramer formation. Surprisingly, the two proximal cysteine residues were dispensable for all these functions, despite their strict evolutionary conservation. Several lines of evidence suggest that the C-terminal CPXC motifs of Cfd1-Nbp35 coordinate a bridging [4Fe-4S] cluster. Upon mutation of the nucleotide binding motifs Fe-S clusters could no longer be assembled on these proteins unless wild-type copies of Cfd1 and Nbp35 were present in trans. This result indicated that Fe-S cluster loading on these scaffold proteins is a nucleotide-dependent step. We propose that the bridging coordination of the C-terminal Fe-S cluster may be ideal for its facile assembly, labile binding, and efficient transfer to target Fe-S apoproteins, a step facilitated by the cytosolic iron-sulfur (Fe-S) protein assembly proteins Nar1 and Cia1 in vivo. PMID:22362766

  13. Modulation of cluster incorporation specificity in a de novo iron-sulfur cluster binding peptide.

    PubMed

    Sommer, Dayn Joseph; Roy, Anindya; Astashkin, Andrei; Ghirlanda, Giovanna

    2015-07-01

    iron-sulfur cluster binding proteins perform an astounding variety of functions, and represent one of the most abundant classes of metalloproteins. Most often, they constitute pairs or chains and act as electron transfer modules either within complex redox enzymes or within small diffusible proteins. We have previously described the design of a three-helix bundle that can bind two clusters within its hydrophobic core. Here, we use single-point mutations to exchange one of the Cys ligands coordinating the cluster to either Leu or Ser. We show that the mutants modulate the redox potential of the clusters and stabilize the [3Fe-4S] form over the [4Fe-4S] form, supporting the use of model iron-sulfur cluster proteins as modules in the design of complex redox enzymes.

  14. Uranium pyrophosphate / methylenediphosphonate polyoxometalate cage clusters

    SciTech Connect

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

    2010-09-29

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

  15. Dynamic multifactor clustering of financial networks

    NASA Astrophysics Data System (ADS)

    Ross, Gordon J.

    2014-02-01

    We investigate the tendency for financial instruments to form clusters when there are multiple factors influencing the correlation structure. Specifically, we consider a stock portfolio which contains companies from different industrial sectors, located in several different countries. Both sector membership and geography combine to create a complex clustering structure where companies seem to first be divided based on sector, with geographical subclusters emerging within each industrial sector. We argue that standard techniques for detecting overlapping clusters and communities are not able to capture this type of structure and show how robust regression techniques can instead be used to remove the influence of both sector and geography from the correlation matrix separately. Our analysis reveals that prior to the 2008 financial crisis, companies did not tend to form clusters based on geography. This changed immediately following the crisis, with geography becoming a more important determinant of clustering structure.

  16. Swarm Intelligence in Text Document Clustering

    SciTech Connect

    Cui, Xiaohui; Potok, Thomas E

    2008-01-01

    Social animals or insects in nature often exhibit a form of emergent collective behavior. The research field that attempts to design algorithms or distributed problem-solving devices inspired by the collective behavior of social insect colonies is called Swarm Intelligence. Compared to the traditional algorithms, the swarm algorithms are usually flexible, robust, decentralized and self-organized. These characters make the swarm algorithms suitable for solving complex problems, such as document collection clustering. The major challenge of today's information society is being overwhelmed with information on any topic they are searching for. Fast and high-quality document clustering algorithms play an important role in helping users to effectively navigate, summarize, and organize the overwhelmed information. In this chapter, we introduce three nature inspired swarm intelligence clustering approaches for document clustering analysis. These clustering algorithms use stochastic and heuristic principles discovered from observing bird flocks, fish schools and ant food forage.

  17. 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.

  18. Globular cluster clustering around ultra compact dwarf galaxies in the halo of NGC 1399

    NASA Astrophysics Data System (ADS)

    Voggel, Karina; Hilker, Michael; Richtler, Tom

    2016-08-01

    We tested the spatial distribution of UCDs and GCs in the halo of NGC 1399 in the Fornax cluster. In particular we tried to find out if globular clusters are more abundant in the vicinity of UCDs than what is expected from their global distribution. A local overabundance of globular clusters was found around UCDs on a scale of 1 kpc compared to what is expected from the large scale distribution of globulars in the host galaxy. This effect is stronger for the metal-poor blue GCs and weaker for the red GCs. An explanation for these clustered globulars is either that they are the remains of a GC system of an ancestor dwarf galaxy before it was stripped to its nucleus, which appears as UCD today. Alternatively these clustered GCs could have been originally part of a super star cluster complex.

  19. Gold-bismuth clusters.

    PubMed

    Martínez, Ana

    2014-08-07

    Metal clusters have interesting characteristics, such as the relationship between properties and size of the cluster. This is not always apparent, so theoretical studies can provide relevant information. In this report, optimized structures and electron donor-acceptor properties of AunBim clusters are reported (n + m = 2-7, 20). Density functional theory calculations were performed to obtain optimized structures. The ground states of gold clusters formed with up to seven atoms are planar. The presence of Bi modifies the structure, and the clusters become 3-D. Several optimized geometries have at least one Bi atom bonded to gold or bismuth atoms and form structures similar to NH3. This fragment is also present in clusters with 20 atoms, where the formation of Au3Bi stabilizes the structures. Bismuth clusters are better electron donors and worse electron acceptors than gold clusters. Mixed clusters fall in between these two extremes. The presence of Bi atoms in gold clusters modifies the electron donor-acceptor properties of the clusters, but there is no correlation between the number of Bi atoms present in the cluster and the capacity for donating electrons. The effect of planarity in Au19Bi clusters is the same as that in Au20 clusters. The properties of pure gold clusters are certainly interesting, but clusters formed by Bi and Au are more important because the introduction of different atoms modifies the geometry, the stability, and consequently the physical and chemical properties. Apparently, the presence of Bi may increase the reactivity of gold clusters, but further studies are necessary to corroborate this hypothesis.

  20. Numerical Flow Visualization in Basic- and Hyper-Cluster Spheres

    NASA Technical Reports Server (NTRS)

    Hendricks, R. C.; Athavale, M. M.; Braun, M. J.; Lattime, S.

    1997-01-01

    Packed spherical particle beds have wide applications throughout the process industry and are usually analyzed using an appropriate combination of laminar and turbulent flows with empirically derived coefficients of which the Ergun (1952) relation is probably the best known. The 3-D complexity of the void distribution within the beds has precluded detailed studies of sphere clusters. Numerical modeling and flow vector visualization for the basic tetra- and hexa-sphere clusters and two hyper-sphere clusters are presented at two Reynolds numbers, 400 and 1200. Cutting planes are used to enable visualization of the complex flows generated within the sphere clusters and are discussed herein. The boundary conditions and flow fields for the simple clusters are also compared to the hyper-clusters with larger variations found for hexa-clusters.

  1. Online clustering algorithms for radar emitter classification.

    PubMed

    Liu, Jun; Lee, Jim P Y; Senior; Li, Lingjie; Luo, Zhi-Quan; Wong, K Max

    2005-08-01

    Radar emitter classification is a special application of data clustering for classifying unknown radar emitters from received radar pulse samples. The main challenges of this task are the high dimensionality of radar pulse samples, small sample group size, and closely located radar pulse clusters. In this paper, two new online clustering algorithms are developed for radar emitter classification: One is model-based using the Minimum Description Length (MDL) criterion and the other is based on competitive learning. Computational complexity is analyzed for each algorithm and then compared. Simulation results show the superior performance of the model-based algorithm over competitive learning in terms of better classification accuracy, flexibility, and stability.

  2. Interplay of degree correlations and cluster synchronization

    NASA Astrophysics Data System (ADS)

    Jalan, Sarika; Kumar, Anil; Zaikin, Alexey; Kurths, Jürgen

    2016-12-01

    We study the evolution of coupled chaotic dynamics on networks and investigate the role of degree-degree correlation in the networks' cluster synchronizability. We find that an increase in the disassortativity can lead to an increase or a decrease in the cluster synchronizability depending on the degree distribution and average connectivity of the network. Networks with heterogeneous degree distribution exhibit significant changes in cluster synchronizability as well as in the phenomena behind cluster synchronization as compared to those of homogeneous networks. Interestingly, cluster synchronizability of a network may be very different from global synchronizability due to the presence of the driven phenomenon behind the cluster formation. Furthermore, we show how degeneracy at the zero eigenvalues provides an understanding of the occurrence of the driven phenomenon behind the synchronization in disassortative networks. The results demonstrate the importance of degree-degree correlations in determining cluster synchronization behavior of complex networks and hence have potential applications in understanding and predicting dynamical behavior of complex systems ranging from brain to social systems.

  3. Nuclear Clusters in Astrophysics

    NASA Astrophysics Data System (ADS)

    Kubono, S.; Binh, Dam N.; Hayakawa, S.; Hashimoto, H.; Kahl, D.; Wakabayashi, Y.; Yamaguchi, H.; Teranishi, T.; Iwasa, N.; Komatsubara, T.; Kato, S.; Khiem, Le H.

    2010-03-01

    The role of nuclear clustering is discussed for nucleosynthesis in stellar evolution with Cluster Nucleosynthesis Diagram (CND) proposed before. Special emphasis is placed on α-induced stellar reactions together with molecular states for O and C burning.

  4. Matlab Cluster Ensemble Toolbox

    SciTech Connect

    Sapio, Vincent De; Kegelmeyer, Philip

    2009-04-27

    This is a Matlab toolbox for investigating the application of cluster ensembles to data classification, with the objective of improving the accuracy and/or speed of clustering. The toolbox divides the cluster ensemble problem into four areas, providing functionality for each. These include, (1) synthetic data generation, (2) clustering to generate individual data partitions and similarity matrices, (3) consensus function generation and final clustering to generate ensemble data partitioning, and (4) implementation of accuracy metrics. With regard to data generation, Gaussian data of arbitrary dimension can be generated. The kcenters algorithm can then be used to generate individual data partitions by either, (a) subsampling the data and clustering each subsample, or by (b) randomly initializing the algorithm and generating a clustering for each initialization. In either case an overall similarity matrix can be computed using a consensus function operating on the individual similarity matrices. A final clustering can be performed and performance metrics are provided for evaluation purposes.

  5. [Pathophysiology of cluster headache].

    PubMed

    Donnet, Anne

    2015-11-01

    The aetiology of cluster headache is partially unknown. Three areas are involved in the pathogenesis of cluster headache: the trigeminal nociceptive pathways, the autonomic system and the hypothalamus. The cluster headache attack involves activation of the trigeminal autonomic reflex. A dysfunction located in posterior hypothalamic gray matter is probably pivotal in the process. There is a probable association between smoke exposure, a possible genetic predisposition and the development of cluster headache.

  6. Resonant nano-cluster devices.

    PubMed

    Haglmüller, J; Rauter, H; Bauer, G; Pittner, F; Schalkhammer, T

    2005-04-01

    The resonance-enhanced absorption (REA) by metal clusters on a surface is an effective technique on which to base bio-optical devices. A four-layer device consisting of a metal mirror, a polymer or glass-type distance layer, a biomolecule interaction layer and a sub-monolayer of biorecognitively bound metal nano-clusters is reported. Experiments indicate a strong influence of the resonator homogeneity on the absorption maximum. Layer stability plays an important role in the overall performance of the device. Techniques and optimised lab protocols to set up biochips that use the REA process in the detection are presented. The sensors show one to three narrow reflection minima in the visible and or infra-red (IR) part of the spectrum and therefore they do not suffer from the spectral limitations associated with spherical gold colloids. Metal clusters (synthesised by thermal step reduction) as well as metal- dielectric shell clusters (synthesised by various shell deposition processes) are used to precisely shift the readout of the device to any frequency in the visible and near IR range. Disposable single-step protein chips, DNA assays as well as complex biochip arrays are established that use various DNARNA, antigen-antibody and protein-protein interaction systems.

  7. Clustering algorithm studies

    NASA Astrophysics Data System (ADS)

    Graf, Norman A.

    2001-07-01

    An object-oriented framework for undertaking clustering algorithm studies has been developed. We present here the definitions for the abstract Cells and Clusters as well as the interface for the algorithm. We intend to use this framework to investigate the interplay between various clustering algorithms and the resulting jet reconstruction efficiency and energy resolutions to assist in the design of the calorimeter detector.

  8. Spatial and kinematic segregation in star-cluster merger remnants

    NASA Astrophysics Data System (ADS)

    Cole, David R.; Debattista, Victor P.; Varri, Anna-Lisa; Adam, Markus; Seth, Anil C.

    2017-04-01

    Globular clusters that exhibit chemical and dynamical complexity have been suggested to be the stripped nuclei of dwarf galaxies(e.g. M54, ω Cen). We use N-body simulations of nuclear star clusters forming via the mergers of star clusters to explore the persistence of substructure in the phase space. We find that the observed level of differentiation is difficult to reconcile with the observed if nuclear clusters form wholly out of the mergers of star clusters. Only the star clusters that merged most recently retain sufficiently distinct density and kinematics to be distinguishable from the rest of the nuclear cluster. In situ star formation must therefore be included to explain the observed properties of nuclear star clusters, in good agreement with previous results.

  9. Star clusters as simple stellar populations.

    PubMed

    Bruzual A, Gustavo

    2010-02-28

    In this paper, I review to what extent we can understand the photometric properties of star clusters, and of low-mass, unresolved galaxies, in terms of population-synthesis models designed to describe 'simple stellar populations' (SSPs), i.e. groups of stars born at the same time, in the same volume of space and from a gas cloud of homogeneous chemical composition. The photometric properties predicted by these models do not readily match the observations of most star clusters, unless we properly take into account the expected variation in the number of stars occupying sparsely populated evolutionary stages, owing to stochastic fluctuations in the stellar initial mass function. In this case, population-synthesis models reproduce remarkably well the full ranges of observed integrated colours and absolute magnitudes of star clusters of various ages and metallicities. The disagreement between the model predictions and observations of cluster colours and magnitudes may indicate problems with or deficiencies in the modelling, and does not necessarily tell us that star clusters do not behave like SSPs. Matching the photometric properties of star clusters using SSP models is a necessary (but not sufficient) condition for clusters to be considered SSPs. Composite models, characterized by complex star-formation histories, also match the observed cluster colours.

  10. Cremmer–Gervais cluster structure on SLn

    PubMed Central

    Gekhtman, Michael; Shapiro, Michael; Vainshtein, Alek

    2014-01-01

    We study natural cluster structures in the rings of regular functions on simple complex Lie groups and Poisson–Lie structures compatible with these cluster structures. According to our main conjecture, each class in the Belavin–Drinfeld classification of Poisson–Lie structures on G corresponds to a cluster structure in O(G). We have shown before that this conjecture holds for any G in the case of the standard Poisson–Lie structure and for all Belavin–Drinfeld classes in SLn, n<5. In this paper we establish it for the Cremmer–Gervais Poisson–Lie structure on SLn, which is the least similar to the standard one. Besides, we prove that on SL3 the cluster algebra and the upper cluster algebra corresponding to the Cremmer–Gervais cluster structure do not coincide, unlike the case of the standard cluster structure. Finally, we show that the positive locus with respect to the Cremmer–Gervais cluster structure is contained in the set of totally positive matrices. PMID:24982188

  11. 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.

  12. Star cluster dynamics.

    PubMed

    Vesperini, Enrico

    2010-02-28

    Dynamical evolution plays a key role in shaping the current properties of star clusters and star cluster systems. A detailed understanding of the effects of evolutionary processes is essential to be able to disentangle the properties that result from dynamical evolution from those imprinted at the time of cluster formation. In this review, I focus my attention on globular clusters, and review the main physical ingredients driving their early and long-term evolution, describe the possible evolutionary routes and show how cluster structure and stellar content are affected by dynamical evolution.

  13. [[Cu(en)(2)](2)Re(4)Te(4)(CN)(12)].5H(2)O and [[Cu(en)(2)](2)Re(6)Te(8)(CN)(6)].5H(2)O: bonding of a transition-metal complex to a rhenium chalcocyanide cluster.

    PubMed

    Mironov, Y V; Fedorov, V E; Ijjaali, I; Ibers, J A

    2001-11-19

    The use of a cyano group of a transition-metal cluster complex to bond to another transition-metal complex has been realized in the syntheses of [[Cu(en)(2)](2)Re(4)Te(4)(CN)(12)].5H(2)O (1) and [[Cu(en)(2)](2)Re(6)Te(8)(CN)(6)].5H(2)O (2), (en = ethylenediamine). These compounds have been synthesized by the reaction of an aqueous solution of K(4)[Re(4)Te(4)(CN)(12)].5H(2)O (for 1) or K(4)[Re(6)Te(8)(CN)(6)] (for 2) with an ammonia solution of Cu(en)(2)Cl(2). In each compound, two Cu(en)(2) groups are bonded to the Re cluster through Cu-N(cyanide) bonds. In compound 1, which contains a tetrahedral cluster core, the Cu(en)(2) groups are necessarily bonded to cis cyano groups; in compound 2, which has an octahedral cluster core, they are bonded to trans cyano groups. Compound 1 crystallizes in the monoclinic space group C2/c with four formulas in unit cell of dimensions a = 18.9077(10), b = 15.4841(8), c = 14.4483(8) A, beta = 95.124(1) degrees, and V = 4213.1(4) A(3) (T = 153 K); compound 2 crystallizes in the triclinic space group P1 with one formula in a unit cell of dimensions a = 9.4906(3), b = 10.6529(4), c = 12. 6252(5) A, alpha = 113.599(1) degrees, beta = 103.404(1) degrees, gamma = 92.659(1) degrees, and V = 1123.87(7) A(3) (T = 153 K).

  14. Unconventional methods for clustering

    NASA Astrophysics Data System (ADS)

    Kotyrba, Martin

    2016-06-01

    Cluster analysis or clustering is a task of grouping a set of objects in such a way that objects in the same group (called a cluster) are more similar (in some sense or another) to each other than to those in other groups (clusters). It is the main task of exploratory data mining and a common technique for statistical data analysis used in many fields, including machine learning, pattern recognition, image analysis, information retrieval, and bioinformatics. The topic of this paper is one of the modern methods of clustering namely SOM (Self Organising Map). The paper describes the theory needed to understand the principle of clustering and descriptions of algorithm used with clustering in our experiments.

  15. Improved Ant Colony Clustering Algorithm and Its Performance Study

    PubMed Central

    Gao, Wei

    2016-01-01

    Clustering analysis is used in many disciplines and applications; it is an important tool that descriptively identifies homogeneous groups of objects based on attribute values. The ant colony clustering algorithm is a swarm-intelligent method used for clustering problems that is inspired by the behavior of ant colonies that cluster their corpses and sort their larvae. A new abstraction ant colony clustering algorithm using a data combination mechanism is proposed to improve the computational efficiency and accuracy of the ant colony clustering algorithm. The abstraction ant colony clustering algorithm is used to cluster benchmark problems, and its performance is compared with the ant colony clustering algorithm and other methods used in existing literature. Based on similar computational difficulties and complexities, the results show that the abstraction ant colony clustering algorithm produces results that are not only more accurate but also more efficiently determined than the ant colony clustering algorithm and the other methods. Thus, the abstraction ant colony clustering algorithm can be used for efficient multivariate data clustering. PMID:26839533

  16. Improved Ant Colony Clustering Algorithm and Its Performance Study.

    PubMed

    Gao, Wei

    2016-01-01

    Clustering analysis is used in many disciplines and applications; it is an important tool that descriptively identifies homogeneous groups of objects based on attribute values. The ant colony clustering algorithm is a swarm-intelligent method used for clustering problems that is inspired by the behavior of ant colonies that cluster their corpses and sort their larvae. A new abstraction ant colony clustering algorithm using a data combination mechanism is proposed to improve the computational efficiency and accuracy of the ant colony clustering algorithm. The abstraction ant colony clustering algorithm is used to cluster benchmark problems, and its performance is compared with the ant colony clustering algorithm and other methods used in existing literature. Based on similar computational difficulties and complexities, the results show that the abstraction ant colony clustering algorithm produces results that are not only more accurate but also more efficiently determined than the ant colony clustering algorithm and the other methods. Thus, the abstraction ant colony clustering algorithm can be used for efficient multivariate data clustering.

  17. The C4 clustering algorithm: Clusters of galaxies in the Sloan Digital Sky Survey

    SciTech Connect

    Miller, Christopher J.; Nichol, Robert; Reichart, Dan; Wechsler, Risa H.; Evrard, August; Annis, James; McKay, Timothy; Bahcall, Neta; Bernardi, Mariangela; Boehringer, Hans; Connolly, Andrew; Goto, Tomo; Kniazev, Alexie; Lamb, Donald; Postman, Marc; Schneider, Donald; Sheth, Ravi; Voges, Wolfgang; /Cerro-Tololo InterAmerican Obs. /Portsmouth U., ICG /North Carolina U. /Chicago U., Astron. Astrophys. Ctr. /Chicago U., EFI /Michigan U. /Fermilab /Princeton U. Observ. /Garching, Max Planck Inst., MPE /Pittsburgh U. /Tokyo U., ICRR /Baltimore, Space Telescope Sci. /Penn State U. /Chicago U. /Stavropol, Astrophys. Observ. /Heidelberg, Max Planck Inst. Astron. /INI, SAO

    2005-03-01

    exclude clusters embedded in complex large-scale environments, we find that the velocity dispersion of the remaining clusters is as good an estimator of M{sub 200} as L{sub r}. The final C4 catalog will contain {approx_equal} 2500 clusters using the full SDSS data set and will represent one of the largest and most homogeneous samples of local clusters.

  18. Dynamically allocated virtual clustering management system

    NASA Astrophysics Data System (ADS)

    Marcus, Kelvin; Cannata, Jess

    2013-05-01

    The U.S Army Research Laboratory (ARL) has built a "Wireless Emulation Lab" to support research in wireless mobile networks. In our current experimentation environment, our researchers need the capability to run clusters of heterogeneous nodes to model emulated wireless tactical networks where each node could contain a different operating system, application set, and physical hardware. To complicate matters, most experiments require the researcher to have root privileges. Our previous solution of using a single shared cluster of statically deployed virtual machines did not sufficiently separate each user's experiment due to undesirable network crosstalk, thus only one experiment could be run at a time. In addition, the cluster did not make efficient use of our servers and physical networks. To address these concerns, we created the Dynamically Allocated Virtual Clustering management system (DAVC). This system leverages existing open-source software to create private clusters of nodes that are either virtual or physical machines. These clusters can be utilized for software development, experimentation, and integration with existing hardware and software. The system uses the Grid Engine job scheduler to efficiently allocate virtual machines to idle systems and networks. The system deploys stateless nodes via network booting. The system uses 802.1Q Virtual LANs (VLANs) to prevent experimentation crosstalk and to allow for complex, private networks eliminating the need to map each virtual machine to a specific switch port. The system monitors the health of the clusters and the underlying physical servers and it maintains cluster usage statistics for historical trends. Users can start private clusters of heterogeneous nodes with root privileges for the duration of the experiment. Users also control when to shutdown their clusters.

  19. Cluster randomized trials for pharmacy practice research.

    PubMed

    Gums, Tyler; Carter, Barry; Foster, Eric

    2016-06-01

    Introduction Cluster randomized trials (CRTs) are now the gold standard in health services research, including pharmacy-based interventions. Studies of behaviour, epidemiology, lifestyle modifications, educational programs, and health care models are utilizing the strengths of cluster randomized analyses. Methodology The key property of CRTs is the unit of randomization (clusters), which may be different from the unit of analysis (individual). Subject sample size and, ideally, the number of clusters is determined by the relationship of between-cluster and within-cluster variability. The correlation among participants recruited from the same cluster is known as the intraclass correlation coefficient (ICC). Generally, having more clusters with smaller ICC values will lead to smaller sample sizes. When selecting clusters, stratification before randomization may be useful in decreasing imbalances between study arms. Participant recruitment methods can differ from other types of randomized trials, as blinding a behavioural intervention cannot always be done. When to use CRTs can yield results that are relevant for making "real world" decisions. CRTs are often used in non-therapeutic intervention studies (e.g. change in practice guidelines). The advantages of CRT design in pharmacy research have been avoiding contamination and the generalizability of the results. A large CRT that studied physician-pharmacist collaborative management of hypertension is used in this manuscript as a CRT example. The trial, entitled Collaboration Among Pharmacists and physicians To Improve Outcomes Now (CAPTION), was implemented in primary care offices in the United States for hypertensive patients. Limitations CRT design limitations include the need for a large number of clusters, high costs, increased training, increased monitoring, and statistical complexity.

  20. 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).

  1. In vivo iron–sulfur cluster formation

    PubMed Central

    Raulfs, Estella C.; O'Carroll, Ina P.; Dos Santos, Patricia C.; Unciuleac, Mihaela-Carmen; Dean, Dennis R.

    2008-01-01

    It has been proposed that iron–sulfur [Fe-S] clusters destined for the maturation of [Fe-S] proteins can be preassembled on a molecular scaffold designated IscU. In the present article, it is shown that production of the intact Azotobacter vinelandii [Fe-S] cluster biosynthetic machinery at levels exceeding the amount required for cellular maturation of [Fe-S] proteins results in the accumulation of: (i) apo-IscU, (ii) an oxygen-labile [2Fe-2S] cluster-loaded form of IscU, and (iii) IscU complexed with the S-delivery protein, IscS. It is suggested that these species represent different stages of the [Fe-S] cluster assembly process. Substitution of the IscU Asp39 residue by Ala results in the in vivo trapping of a stoichiometric, noncovalent, nondissociating IscU–IscS complex that contains an oxygen-resistant [Fe-S] species. In aggregate, these results validate the scaffold hypothesis for [Fe-S] cluster assembly and indicate that in vivo [Fe-S] cluster formation is a dynamic process that involves the reversible interaction of IscU and IscS. PMID:18562278

  2. Alkali Metal Cluster Theory.

    NASA Astrophysics Data System (ADS)

    Chen, Jian

    Available from UMI in association with The British Library. Requires signed TDF. In this thesis, we apply the tight-binding Hubbard model to alkali metal clusters with Hartree-Fock self-consistent methods and perturbation methods for the numerical calculations. We have studied the relation between the equilibrium structures and the range of the hopping matrix elements in the Hubbard Hamiltonian. The results show that the structures are not sensitive to the interaction range but are determined by the number of valence electrons each atom has. Inertia tensors are used to analyse the symmetries of the clusters. The principal axes of the clusters are determined and they are the axes of rotational symmetries of clusters if the clusters have any. The eigenvalues of inertia tensors which are the indication of the deformation of clusters are compared between our model and the ellipsoidal jellium model. The agreement is good for large clusters. At a finite temperature, the thermal motion fluctuates the structures. We defined a fluctuation function with the distance matrix of a cluster. The fluctuation has been studied with the Monte-Carlo simulation method. Our studies show that the clusters remain in the solid state when temperature is low. The small values of fluctuation functions indicates the thermal vibration of atoms around their equilibrium positions. If the temperature is high, the atoms are delocalized. The cluster melts and enters the liquid region. The cluster melting is simulated by the Monte-Carlo simulation with the fluctuation function we defined. Energy levels of clusters are calculated from the Hubbard model. Ionization potentials and magic numbers are also obtained from these energy levels. The results confirm that the Hubbard model is a good approximation for a small cluster. The excitation energy is presented by the difference between the original level and excited level, and the electron-hole interactions. We also have studied cooling of clusters

  3. A Perfect Starburst Cluster made in One Go: The NGC 3603 Young Cluster

    NASA Astrophysics Data System (ADS)

    Banerjee, Sambaran; Kroupa, Pavel

    2014-06-01

    Understanding how distinct, near-spherical gas-free clusters of very young, massive stars shape out of vast, complex clouds of molecular hydrogen is one of the biggest challenges in astrophysics. A popular thought dictates that a single gas cloud fragments into many newborn stars which, in turn, energize and rapidly expel the residual gas to form a gas-free cluster. This study demonstrates that the above classical paradigm remarkably reproduces the well-observed central, young cluster (HD 97950) of the Galactic NGC 3603 star-forming region, in particular, its shape, internal motion, and mass distribution of stars naturally and consistently follow from a single model calculation. Remarkably, the same parameters (star formation efficiency, gas expulsion timescale, and delay) reproduce HD 97950, as were found to reproduce the Orion Nebula Cluster, Pleiades, and R136. The present results therefore provide intriguing evidence of formation of star clusters through single-starburst events followed by significant residual gas expulsion.

  4. A perfect starburst cluster made in one go: The NGC 3603 young cluster

    SciTech Connect

    Banerjee, Sambaran; Kroupa, Pavel

    2014-06-01

    Understanding how distinct, near-spherical gas-free clusters of very young, massive stars shape out of vast, complex clouds of molecular hydrogen is one of the biggest challenges in astrophysics. A popular thought dictates that a single gas cloud fragments into many newborn stars which, in turn, energize and rapidly expel the residual gas to form a gas-free cluster. This study demonstrates that the above classical paradigm remarkably reproduces the well-observed central, young cluster (HD 97950) of the Galactic NGC 3603 star-forming region, in particular, its shape, internal motion, and mass distribution of stars naturally and consistently follow from a single model calculation. Remarkably, the same parameters (star formation efficiency, gas expulsion timescale, and delay) reproduce HD 97950, as were found to reproduce the Orion Nebula Cluster, Pleiades, and R136. The present results therefore provide intriguing evidence of formation of star clusters through single-starburst events followed by significant residual gas expulsion.

  5. Multi-level coupled cluster theory

    SciTech Connect

    Myhre, Rolf H.; Koch, Henrik; Sánchez de Merás, Alfredo M. J.

    2014-12-14

    We present a general formalism where different levels of coupled cluster theory can be applied to different parts of the molecular system. The system is partitioned into subsystems by Cholesky decomposition of the one-electron Hartree-Fock density matrix. In this way the system can be divided across chemical bonds without discontinuities arising. The coupled cluster wave function is defined in terms of cluster operators for each part and these are determined from a set of coupled equations. The total wave function fulfills the Pauli-principle across all borders and levels of electron correlation. We develop the associated response theory for this multi-level coupled cluster theory and present proof of principle applications. The formalism is an essential tool in order to obtain size-intensive complexity in the calculation of local molecular properties.

  6. Information-based clustering

    PubMed Central

    Slonim, Noam; Atwal, Gurinder Singh; Tkačik, Gašper; Bialek, William

    2005-01-01

    In an age of increasingly large data sets, investigators in many different disciplines have turned to clustering as a tool for data analysis and exploration. Existing clustering methods, however, typically depend on several nontrivial assumptions about the structure of data. Here, we reformulate the clustering problem from an information theoretic perspective that avoids many of these assumptions. In particular, our formulation obviates the need for defining a cluster “prototype,” does not require an a priori similarity metric, is invariant to changes in the representation of the data, and naturally captures nonlinear relations. We apply this approach to different domains and find that it consistently produces clusters that are more coherent than those extracted by existing algorithms. Finally, our approach provides a way of clustering based on collective notions of similarity rather than the traditional pairwise measures. PMID:16352721

  7. Clusters of galaxies

    NASA Astrophysics Data System (ADS)

    Vikhlinin, A. A.; Kravtsov, A. V.; Markevich, M. L.; Sunyaev, R. A.; Churazov, E. M.

    2014-04-01

    Galaxy clusters are formed via nonlinear growth of primordial density fluctuations and are the most massive gravitationally bound objects in the present Universe. Their number density at different epochs and their properties depend strongly on the properties of dark matter and dark energy, making clusters a powerful tool for observational cosmology. Observations of the hot gas filling the gravitational potential well of a cluster allows studying gasdynamic and plasma effects and the effect of supermassive black holes on the heating and cooling of gas on cluster scales. The work of Yakov Borisovich Zeldovich has had a profound impact on virtually all cosmological and astrophysical studies of galaxy clusters, introducing concepts such as the Harrison-Zeldovich spectrum, the Zeldovich approximation, baryon acoustic peaks, and the Sunyaev-Zeldovich effect. Here, we review the most basic properties of clusters and their role in modern astrophysics and cosmology.

  8. Multi-viewpoint clustering analysis

    NASA Technical Reports Server (NTRS)

    Mehrotra, Mala; Wild, Chris

    1993-01-01

    In this paper, we address the feasibility of partitioning rule-based systems into a number of meaningful units to enhance the comprehensibility, maintainability and reliability of expert systems software. Preliminary results have shown that no single structuring principle or abstraction hierarchy is sufficient to understand complex knowledge bases. We therefore propose the Multi View Point - Clustering Analysis (MVP-CA) methodology to provide multiple views of the same expert system. We present the results of using this approach to partition a deployed knowledge-based system that navigates the Space Shuttle's entry. We also discuss the impact of this approach on verification and validation of knowledge-based systems.

  9. Chemistry Within Molecular Clusters

    DTIC Science & Technology

    1990-01-01

    DME )nCH3OCH 2 +). We speculate that this is due to the fragments being consumed by an ion-molecule reaction within the cluster. One likely candidate is...the ion-molecule reaction of the fragment cations with a neutral DME , within the bulk cluster to form a trimethyloxonlum cation intermediate. This...the observed products. We therefore speculate that the DME cluster reactions leading to the same products, should involve the same mechanism found to

  10. Chemistry Within Molecular Clusters

    DTIC Science & Technology

    1992-06-01

    and ( DME ).CH 3OCH2+). We speculate that this is due to the fragments being consumed by an ion-molecule reaction within the cluster. A likely candidate...is the ion-molecule reaction of the fragment cations with a neutral DME within the bulk cluster, to form a trimethyloxonium cation intermediate...a trimethyloxonium intermediate as the common intermediate for the observed products. We therefore speculate that the DME cluster reactions leading to

  11. Cluster State Quantum Computation

    DTIC Science & Technology

    2014-02-01

    nearest neighbor cluster state has been shown to be a universal resource for MBQC thus we can say our quantum computer is universal. We note that...CLUSTER STATE QUANTUM COMPUTATION FEBRUARY 2014 FINAL TECHNICAL REPORT APPROVED FOR PUBLIC RELEASE; DISTRIBUTION UNLIMITED STINFO COPY AIR FORCE...TITLE AND SUBTITLE CLUSTER STATE QUANTUM COMPUTATION 5a. CONTRACT NUMBER IN-HOUSE 5b. GRANT NUMBER N/A 5c. PROGRAM ELEMENT NUMBER 62788F 6

  12. Chemical Reactions in Clusters

    DTIC Science & Technology

    1992-11-04

    NH 3)n, n _> 4, clusters has been attributed to the (solvated) naphtholate anion.3a A single picosecond decay measurement has been reported which...vibrational energy in the cluster Sl state. The data are summarized in Table I. A model to explain these decay results can be constructed based on a proton...11 TITLE (Include Security Classification) Chemical Reactions in Clusters 12 PERSONAL AUTHOR(S) Elliot R. Bernstein 13a TYPE OF REPORT 13b TIME COVERED

  13. 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.

  14. Melting of nickel clusters

    SciTech Connect

    Garzon, I.L.; Jellinek, J.

    1991-12-31

    The meltinglike phenomenon in Ni{sub n}, n = 19,20,55, clusters is studied using microcanonical molecular dynamics simulations. The interaction between the atoms in the clusters is modelled by a size-dependent Gupta-like potential that incorporates many-body effects. The clusters display the ``usual`` stages in their meltinglike transition, which characterize also Lennard-Jones (e.g., noble gas) and ionic clusters. In addition, Ni{sub 20} passes through a so-called premelting stage found earlier also for Ni{sub 14}. 11 ref., 3 figs.

  15. Melting of nickel clusters

    SciTech Connect

    Garzon, I.L. . Inst. de Fisica); Jellinek, J. )

    1991-01-01

    The meltinglike phenomenon in Ni{sub n}, n = 19,20,55, clusters is studied using microcanonical molecular dynamics simulations. The interaction between the atoms in the clusters is modelled by a size-dependent Gupta-like potential that incorporates many-body effects. The clusters display the usual'' stages in their meltinglike transition, which characterize also Lennard-Jones (e.g., noble gas) and ionic clusters. In addition, Ni{sub 20} passes through a so-called premelting stage found earlier also for Ni{sub 14}. 11 ref., 3 figs.

  16. 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.

  17. Clustering versus non-clustering phase synchronizations

    SciTech Connect

    Liu, Shuai; Zhan, Meng

    2014-03-15

    Clustering phase synchronization (CPS) is a common scenario to the global phase synchronization of coupled dynamical systems. In this work, a novel scenario, the non-clustering phase synchronization (NPS), is reported. It is found that coupled systems do not transit to the global synchronization until a certain sufficiently large coupling is attained, and there is no clustering prior to the global synchronization. To reveal the relationship between CPS and NPS, we further analyze the noise effect on coupled phase oscillators and find that the coupled oscillator system can change from CPS to NPS with the increase of noise intensity or system disorder. These findings are expected to shed light on the mechanism of various intriguing self-organized behaviors in coupled systems.

  18. A nonparametric clustering technique which estimates the number of clusters

    NASA Technical Reports Server (NTRS)

    Ramey, D. B.

    1983-01-01

    In applications of cluster analysis, one usually needs to determine the number of clusters, K, and the assignment of observations to each cluster. A clustering technique based on recursive application of a multivariate test of bimodality which automatically estimates both K and the cluster assignments is presented.

  19. Beowulf Cluster for Computational Corrosion and Catalysis Studies

    DTIC Science & Technology

    2007-11-02

    This DURIP-funded Beowulf cluster will enhance our AFOSR-funded research in several areas. Large-scale modeling of complex systems in the areas of...high accuracy on real-world systems requires significant computational cost. This grant, by funding a Beowulf cluster supercomputing environment, has

  20. Spanish Dyslexic Spelling Abilities: The Case of Consonant Clusters

    ERIC Educational Resources Information Center

    Serrano, Francisca; Defior, Sylvia

    2012-01-01

    This paper investigates Spanish dyslexic spelling abilities: specifically, the influence of syllabic linguistic structure (simple vs consonant cluster) on children's spelling performance. Consonant clusters are phonologically complex structures, so it was anticipated that there would be lower spelling performance for these syllabic structures than…

  1. Exploring the correlation between network structure and electron binding energy in the (H2O)7- cluster through isomer-photoselected vibrational predissociation spectroscopy and ab initio calculations: Addressing complexity beyond types I-III

    NASA Astrophysics Data System (ADS)

    Roscioli, Joseph R.; Hammer, Nathan I.; Johnson, Mark A.; Diri, Kadir; Jordan, Kenneth D.

    2008-03-01

    We report a combined photoelectron and vibrational spectroscopy study of the (H2O)7- cluster anions in order to correlate structural changes with the observed differences in electron binding energies of the various isomers. Photoelectron spectra of the (H2O)7-ṡArm clusters are obtained over the range of m =0-10. These spectra reveal the formation of a new isomer (I') for m >5, the electron binding energy of which is about 0.15eV higher than that of the type I form previously reported to be the highest binding energy species [Coe et al., J. Chem. Phys. 92, 3980 (1990)]. Isomer-selective vibrational predissociation spectra are obtained using both the Ar dependence of the isomer distribution and photochemical depopulation of the more weakly (electron) binding isomers. The likely structures of the isomers at play are identified with the aid of electronic structure calculations, and the electron binding energies, as well as harmonic vibrational spectra, are calculated for 28 low-lying forms for comparison with the experimental results. The HOH bending spectrum of the low binding type II form is dominated by a band that is moderately redshifted relative to the bending origin of the bare water molecule. Calculations trace this feature primarily to the bending vibration localized on a water molecule in which a dangling H atom points toward the electron cloud. Both higher binding forms (I and I') display the characteristic patterns in the bending and OH stretching regions signaling electron attachment primarily to a water molecule in an AA binding site, a persistent motif found in non-isomer-selective spectra of the clusters up to (H2O)50-.

  2. Site specific ligand substitution in cubane-type Mo3FeS(4)(4+) clusters: kinetics and mechanism of reaction and isolation of mixed ligand Cl/SPh complexes.

    PubMed

    Algarra, Andrés G; Basallote, Manuel G; Fernandez-Trujillo, M J; Llusar, Rosa; Pino-Chamorro, Jose A; Sorribes, Ivan; Vicent, Cristian

    2010-04-21

    The synthesis, crystal structure and solution characterization of the cubane-type [Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3)] (1) (dmpe = 1,2-bis(dimethylphophane-ethane)) cluster are reported and the ligand substitution processes of chloride by thiophenolate investigated. The kinetics and the intimate mechanism of these substitutions reveal that compound 1 undergoes a number of Fe and Mo site specific ligand substitution reactions in acetonitrile solutions. In particular, PhS(-) coordination at the tetrahedral Fe site proceeds in a single resolved kinetic step whereas such substitutions at the Mo sites proceed more slowly. The effect of the presence of acids in the reaction media is also investigated and reveals that an acid excess hinders substitution reactions both at the Fe and Mo sites; however, an acid-promoted solvolysis of the Fe-Cl bonds is observed. Electrospray ionization (ESI) and tandem (ESI-MS/MS) mass spectrometry allow the identification of all the reaction intermediates proposed on the basis of stopped-flow measurements. The distinctive site specific reactivity made it possible to isolate two new clusters of the Mo(3)FeS(4)(4+) family featuring mixed chlorine/thiophenolate ligands, namely Mo(3)S(4)(FeSPh)(dmpe)(3)Cl(3) (2) and [Mo(3)S(4)(FeSPh)(dmpe)(3)(SPh)(3)] (3). A detailed computational study has also been carried out to understand the details of the mechanism of substitution at the M-Cl (M = Mo and Fe) bonds as well as the solvolysis at the Fe-Cl sites, with particular emphasis on the role of acids on the substitution process. The results of the calculations are in agreement with the experimental observations, thus justifying the non-existence of an accelerating effect of acids on the thiophenolate substitution reaction, which differs from previous proposals for the Fe(4)S(4) and MoFe(3)S(4) clusters and some related compounds.

  3. Structure and dynamics of cationic van-der-Waals clusters. II. Dynamics of protonated argon clusters

    NASA Astrophysics Data System (ADS)

    Ritschel, T.; Zuhrt, Ch.; Zülicke, L.; Kuntz, P. J.

    2007-01-01

    A diatomics-in-molecules (DIM) model with ab-initio input data, which in part I successfully described the structure and bonding properties of protonated argon clusters ArnH+, is used here to investigate some aspects of the dynamics of such aggregates for n up to 30. The simple triatomic ionic fragment, Ar2H+, is studied in some detail with respect to normal vibrations, characteristics of classical intramolecular dynamics as reflected in the Fourier spectra of dynamical variables, and accurate quantum states of the vibrational motion. For larger clusters ArnH+ (n ≤30), the normal vibrational frequencies (and displacement eigenvectors) are calculated and related to the cluster structure. In addition, the Fourier spectra are analyzed with respect to their variation with changing internal energy and cluster size. As expected, the clusters show some floppy character. Even a little vibrational excitation can lead to internal rearrangement and to Ar-atom evaporation from the clusters; this is studied in more detail for one small complex (n = 3). Electronic excitation to one of the low-lying excited states, which are all globally repulsive, leads to complete fragmentation (atomization) of the clusters. A variety of conceivable elementary collision processes involving protonated argon clusters are discussed. Some of these may play a role in the gas-phase formation of medium-sized ArnH+ aggregates.

  4. When galaxy clusters collide: the impact of merger shocks on cluster gas and galaxy evolution

    NASA Astrophysics Data System (ADS)

    Stroe, A.

    2015-09-01

    Galaxy clusters mainly grow through mergers with other clusters and groups. Major mergers give rise to cluster-wide traveling shocks, which can be detected at radio wavelengths as relics: elongated, diffuse synchrotron emitting areas located at the periphery of merging clusters. The 'Sausage' cluster hosts an extraordinary Mpc-wide relic, which enables us to study to study particle acceleration and the effects of shocks on cluster galaxies. We derive shock properties and the magnetic field structure for the relic. Our results indicate that particles are shock-accelerated, but turbulent re-acceleration or unusually efficient transport of particles in the downstream area are important effects. We demonstrate the feasibility of high-frequency observations of radio relics, by presenting a 16 GHz detection of the 'Sausage' relic. Halpha mapping of the cluster provides the first direct test as to whether the shock drives or prohibits star formation. We find numerous galaxies in! close proximity to the radio relic which are extremely massive, metal-rich, star-forming with evidence for gas mass loss though outflows. We speculate that the complex interaction between the merger, the shock wave and gas is a fundamental driver in the evolution of cluster galaxies from gas rich spirals to gas-poor ellipticals.

  5. Photoionization of molecular clusters

    NASA Astrophysics Data System (ADS)

    Andres, R. P.; Calo, J. M.

    1981-12-01

    An experimental apparatus consisting of a novel multiple expansion cluster source coupled with a molecular beam system and photoionization mass spectrometer has been designed and constructed. This apparatus has been thoroughly tested and preliminary measurements of the growth kinetics of water clusters and the photoionization cross section of the water dimer have been carried out.

  6. Probability and Cancer Clusters

    ERIC Educational Resources Information Center

    Hamilton-Keene, Rachael; Lenard, Christoper T.; Mills, Terry M.

    2009-01-01

    Recently there have been several news items about possible cancer clusters in the Australian media. The term "cancer cluster" is used when an unusually large number of people in one geographic area, often a workplace, are diagnosed with cancer in a short space of time. In this paper the authors explore this important health issue using…

  7. 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).

  8. Mixed-Initiative Clustering

    ERIC Educational Resources Information Center

    Huang, Yifen

    2010-01-01

    Mixed-initiative clustering is a task where a user and a machine work collaboratively to analyze a large set of documents. We hypothesize that a user and a machine can both learn better clustering models through enriched communication and interactive learning from each other. The first contribution or this thesis is providing a framework of…

  9. Cluster Guide. Accounting Occupations.

    ERIC Educational Resources Information Center

    Beaverton School District 48, OR.

    Based on a recent task inventory of key occupations in the accounting cluster taken in the Portland, Oregon, area, this curriculum guide is intended to assist administrators and teachers in the design and implementation of high school accounting cluster programs. The guide is divided into four major sections: program organization and…

  10. Marketing Occupations. Cluster Guide.

    ERIC Educational Resources Information Center

    Oregon State Dept. of Education, Salem.

    This cluster guide, which is designed to show teachers what specific knowledge and skills qualify high school students for entry-level employment (or postsecondary training) in marketing occupations, is organized into three sections: (1) cluster organization and implementation, (2) instructional emphasis areas, and (3) assessment. The first…

  11. Ultrametric Hierarchical Clustering Algorithms.

    ERIC Educational Resources Information Center

    Milligan, Glenn W.

    1979-01-01

    Johnson has shown that the single linkage and complete linkage hierarchical clustering algorithms induce a metric on the data known as the ultrametric. Johnson's proof is extended to four other common clustering algorithms. Two additional methods also produce hierarchical structures which can violate the ultrametric inequality. (Author/CTM)

  12. [Cluster headache differential diagnosis].

    PubMed

    Guégan-Massardier, Evelyne; Laubier, Cécile

    2015-11-01

    Cluster headache is characterized by disabling stereotyped headache. Early diagnosis allows appropriate treatment, unfortunately diagnostic errors are frequent. The main differential diagnoses are other primary or essential headaches. Migraine, more frequent and whose diagnosis is carried by excess, trigeminal neuralgia or other trigemino-autonomic cephalgia. Vascular or tumoral underlying condition can mimic cluster headache, neck and brain imaging is recommended, ideally MRI.

  13. Targeting Clusters, Achieving Excellence.

    ERIC Educational Resources Information Center

    Rosenfeld, Stuart; Jacobs, Jim; Liston, Cynthia

    2003-01-01

    Suggests that groups, or clusters, of industries form partnerships with community colleges in order to positively impact economic development. Asserts that a cluster-oriented community college system requires innovation, specialized resources and expertise, knowledge of trends, and links to industry. Offers suggestions for developing such a…

  14. Multiple frame cluster tracking

    NASA Astrophysics Data System (ADS)

    Gadaleta, Sabino; Klusman, Mike; Poore, Aubrey; Slocumb, Benjamin J.

    2002-08-01

    Tracking large number of closely spaced objects is a challenging problem for any tracking system. In missile defense systems, countermeasures in the form of debris, chaff, spent fuel, and balloons can overwhelm tracking systems that track only individual objects. Thus, tracking these groups or clusters of objects followed by transitions to individual object tracking (if and when individual objects separate from the groups) is a necessary capability for a robust and real-time tracking system. The objectives of this paper are to describe the group tracking problem in the context of multiple frame target tracking and to formulate a general assignment problem for the multiple frame cluster/group tracking problem. The proposed approach forms multiple clustering hypotheses on each frame of data and base individual frame clustering decisions on the information from multiple frames of data in much the same way that MFA or MHT work for individual object tracking. The formulation of the assignment problem for resolved object tracking and candidate clustering methods for use in multiple frame cluster tracking are briefly reviewed. Then, three different formulations are presented for the combination of multiple clustering hypotheses on each frame of data and the multiple frame assignments of clusters between frames.

  15. Brightest Cluster Galaxy Identification

    NASA Astrophysics Data System (ADS)

    Leisman, Luke; Haarsma, D. B.; Sebald, D. A.; ACCEPT Team

    2011-01-01

    Brightest cluster galaxies (BCGs) play an important role in several fields of astronomical research. The literature includes many different methods and criteria for identifying the BCG in the cluster, such as choosing the brightest galaxy, the galaxy nearest the X-ray peak, or the galaxy with the most extended profile. Here we examine a sample of 75 clusters from the Archive of Chandra Cluster Entropy Profile Tables (ACCEPT) and the Sloan Digital Sky Survey (SDSS), measuring masked magnitudes and profiles for BCG candidates in each cluster. We first identified galaxies by hand; in 15% of clusters at least one team member selected a different galaxy than the others.We also applied 6 other identification methods to the ACCEPT sample; in 30% of clusters at least one of these methods selected a different galaxy than the other methods. We then developed an algorithm that weighs brightness, profile, and proximity to the X-ray peak and centroid. This algorithm incorporates the advantages of by-hand identification (weighing multiple properties) and automated selection (repeatable and consistent). The BCG population chosen by the algorithm is more uniform in its properties than populations selected by other methods, particularly in the relation between absolute magnitude (a proxy for galaxy mass) and average gas temperature (a proxy for cluster mass). This work supported by a Barry M. Goldwater Scholarship and a Sid Jansma Summer Research Fellowship.

  16. Hybridization schemes for clusters

    NASA Astrophysics Data System (ADS)

    Wales, David J.

    The concept of an optimum hybridization scheme for cluster compounds is developed with particular reference to electron counting. The prediction of electron counts for clusters and the interpretation of the bonding is shown to depend critically upon the presumed hybridization pattern of the cluster vertex atoms. This fact has not been properly appreciated in previous work, particularly in applications of Stone's tensor surface harmonic (TSH) theory, but is found to be a useful tool when dealt with directly. A quantitative definition is suggested for the optimum cluster hybridization pattern based directly upon the ease of interpretation of the molecular orbitals, and results are given for a range of species. The relationship of this scheme to the detailed cluster geometry is described using Löwdin's partitioned perturbation theory, and the success and range of application of TSH theory are discussed.

  17. Galaxy cluster's rotation

    NASA Astrophysics Data System (ADS)

    Manolopoulou, M.; Plionis, M.

    2017-03-01

    We study the possible rotation of cluster galaxies, developing, testing, and applying a novel algorithm which identifies rotation, if such does exist, as well as its rotational centre, its axis orientation, rotational velocity amplitude, and, finally, the clockwise or counterclockwise direction of rotation on the plane of the sky. To validate our algorithms we construct realistic Monte Carlo mock rotating clusters and confirm that our method provides robust indications of rotation. We then apply our methodology on a sample of Abell clusters with z ≲ 0.1 with member galaxies selected from the Sloan Digital Sky Survey DR10 spectroscopic data base. After excluding a number of substructured clusters, which could provide erroneous indications of rotation, and taking into account the expected fraction of misidentified coherent substructure velocities for rotation, provided by our Monte Carlo simulation analysis, we find that ∼23 per cent of our clusters are rotating under a set of strict criteria. Loosening the strictness of the criteria, on the expense of introducing spurious rotation indications, we find this fraction increasing to ∼28 per cent. We correlate our rotation indicators with the cluster dynamical state, provided either by their Bautz-Morgan type or by their X-ray isophotal shape and find for those clusters showing rotation within 1.5 h^{-1}_{70} Mpc that the significance of their rotation is related to the dynamically younger phases of cluster formation but after the initial anisotropic accretion and merging has been completed. Finally, finding rotational modes in galaxy clusters could lead to the necessity of correcting the dynamical cluster mass calculations.

  18. Single-Pass Clustering Algorithm Based on Storm

    NASA Astrophysics Data System (ADS)

    Fang, LI; Longlong, DAI; Zhiying, JIANG; Shunzi, LI

    2017-02-01

    The dramatically increasing volume of data makes the computational complexity of traditional clustering algorithm rise rapidly accordingly, which leads to the longer time. So as to improve the efficiency of the stream data clustering, a distributed real-time clustering algorithm (S-Single-Pass) based on the classic Single-Pass [1] algorithm and Storm [2] computation framework was designed in this paper. By employing this kind of method in the Topic Detection and Tracking (TDT) [3], the real-time performance of topic detection arises effectively. The proposed method splits the clustering process into two parts: one part is to form clusters for the multi-thread parallel clustering, the other part is to merge the generated clusters in the previous process and update the global clusters. Through the experimental results, the conclusion can be drawn that the proposed method have the nearly same clustering accuracy as the traditional Single-Pass algorithm and the clustering accuracy remains steady, computing rate increases linearly when increasing the number of cluster machines and nodes (processing threads).

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

    DOEpatents

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

    2009-12-22

    Document clustering methods, document cluster label disambiguation methods, document clustering apparatuses, and articles of manufacture are described. In one aspect, a document clustering method includes providing a document set comprising a plurality of documents, providing a cluster comprising a subset of the documents of the document set, using a plurality of terms of the documents, providing a cluster label indicative of subject matter content of the documents of the cluster, wherein the cluster label comprises a plurality of word senses, and selecting one of the word senses of the cluster label.

  20. Message Passing Framework for Globally Interconnected Clusters

    NASA Astrophysics Data System (ADS)

    Hafeez, M.; Asghar, S.; Malik, U. A.; Rehman, A.; Riaz, N.

    2011-12-01

    In prevailing technology trends it is apparent that the network requirements and technologies will advance in future. Therefore the need of High Performance Computing (HPC) based implementation for interconnecting clusters is comprehensible for scalability of clusters. Grid computing provides global infrastructure of interconnecting clusters consisting of dispersed computing resources over Internet. On the other hand the leading model for HPC programming is Message Passing Interface (MPI). As compared to Grid computing, MPI is better suited for solving most of the complex computational problems. MPI itself is restricted to a single cluster. It does not support message passing over the internet to use the computing resources of different clusters in an optimal way. We propose a model that provides message passing capabilities between parallel applications over the internet. The proposed model is based on Architecture for Java Universal Message Passing (A-JUMP) framework and Enterprise Service Bus (ESB) named as High Performance Computing Bus. The HPC Bus is built using ActiveMQ. HPC Bus is responsible for communication and message passing in an asynchronous manner. Asynchronous mode of communication offers an assurance for message delivery as well as a fault tolerance mechanism for message passing. The idea presented in this paper effectively utilizes wide-area intercluster networks. It also provides scheduling, dynamic resource discovery and allocation, and sub-clustering of resources for different jobs. Performance analysis and comparison study of the proposed framework with P2P-MPI are also presented in this paper.

  1. Statistical Issues in Galaxy Cluster Cosmology

    NASA Technical Reports Server (NTRS)

    Mantz, Adam

    2013-01-01

    The number and growth of massive galaxy clusters are sensitive probes of cosmological structure formation. Surveys at various wavelengths can detect clusters to high redshift, but the fact that cluster mass is not directly observable complicates matters, requiring us to simultaneously constrain scaling relations of observable signals with mass. The problem can be cast as one of regression, in which the data set is truncated, the (cosmology-dependent) underlying population must be modeled, and strong, complex correlations between measurements often exist. Simulations of cosmological structure formation provide a robust prediction for the number of clusters in the Universe as a function of mass and redshift (the mass function), but they cannot reliably predict the observables used to detect clusters in sky surveys (e.g. X-ray luminosity). Consequently, observers must constrain observable-mass scaling relations using additional data, and use the scaling relation model in conjunction with the mass function to predict the number of clusters as a function of redshift and luminosity.

  2. Building the World's Fastest Linux Cluster

    SciTech Connect

    Goldstone, R; Seager, M

    2003-10-24

    Imagine having 2,304 Xeon processors running day and night solving complex problems. With a theoretical peak of 11.2 teraflops, that is just what the MCR cluster at Lawrence Livermore National Labs (LLNL) is doing. Over the past several years, Lawrence Livermore National Laboratory has deployed a series of increasingly large and powerful Intel-based Linux clusters. The most significant of these is a cluster known as the MCR (Multiprogrammactic Capability Resource). With 1,152 Intel Xeon (2.4 GHz) dual-processor nodes from Linux NetworX and a high performance interconnect from Quadrics, LTD., the MCR currently ranks third on the 21st Top 500 Supercomputer Sites List and is the fastest Linux cluster in the world. This feat was accomplished with a total system cost (hardware including maintenance, in-reconnect, global file system storage) of under $14 million. Although production clusters like the MCR are still custom built supercomputers that require as much artistry as skill, the experiences of LLNL have helped clear an important path for other clusters to follow.

  3. Clustering metagenomic sequences with interpolated Markov models

    PubMed Central

    2010-01-01

    Background Sequencing of environmental DNA (often called metagenomics) has shown tremendous potential to uncover the vast number of unknown microbes that cannot be cultured and sequenced by traditional methods. Because the output from metagenomic sequencing is a large set of reads of unknown origin, clustering reads together that were sequenced from the same species is a crucial analysis step. Many effective approaches to this task rely on sequenced genomes in public databases, but these genomes are a highly biased sample that is not necessarily representative of environments interesting to many metagenomics projects. Results We present SCIMM (Sequence Clustering with Interpolated Markov Models), an unsupervised sequence clustering method. SCIMM achieves greater clustering accuracy than previous unsupervised approaches. We examine the limitations of unsupervised learning on complex datasets, and suggest a hybrid of SCIMM and supervised learning method Phymm called PHYSCIMM that performs better when evolutionarily close training genomes are available. Conclusions SCIMM and PHYSCIMM are highly accurate methods to cluster metagenomic sequences. SCIMM operates entirely unsupervised, making it ideal for environments containing mostly novel microbes. PHYSCIMM uses supervised learning to improve clustering in environments containing microbial strains from well-characterized genera. SCIMM and PHYSCIMM are available open source from http://www.cbcb.umd.edu/software/scimm. PMID:21044341

  4. Evolution Properties of Clusters and AXAF Contributions to understanding Clusters

    NASA Technical Reports Server (NTRS)

    Jones, Christine

    1998-01-01

    Our ROSAT survey for distant clusters of galaxies contains the largest solid angle of all ROSAT pointed surveying and thus has sufficient area to test the previously reported cluster evolution. We find significant negative cluster evolution, i.e,, at high redshifts there are fewer luminous clusters than at present. We compare optical cluster properties for the most distant clusters in the ROSAT survey with those measured for nearby clusters. We also present AXAF capabilities and show how AXAF will significantly extend our understanding of cluster properties and their cosmological evolution.

  5. Studies in clustering theory

    NASA Astrophysics Data System (ADS)

    Stell, George

    In recent years the properties of percolation models have been studied intensively. The purpose of our project was to develop a general theory of percolation and clustering between particles of arbitrary size and shape, with arbitrary correlations between them. The goal of such a theory includes the treatment of continuum percolation as well as a novel treatment of lattice percolation. We made substantial progress toward this goal. The quantities basic to a description of clustering, the mean cluster size, mean number of clusters, etc., were developed. Concise formulas were given for the terms in such series, and proved, at least for sufficiently low densities, that the series are absolutely convergent. These series can now be used to construct Pade approximants that will allow one to probe the percolation transition. A scaled-particle theory of percolation was developed which gives analytic approximants for the mean number of clusters in a large class of two and three dimensional percolation models. Although this quantity is essential in many applications, e.g., explaining colligative properties, and interpreting low-angle light-scattering data, no systematic studies of it have been done before this work. Recently carried out detailed computer simulations show that the mean number of clusters is given to high accuracy by several of there approximations. Extensions of this work will allow calculation of the complete cluster size distribution.

  6. Nuclear Star Clusters

    NASA Astrophysics Data System (ADS)

    Neumayer, Nadine

    2017-03-01

    The centers of galaxies host two distinct, compact components: massive black holes and nuclear star clusters. Nuclear star clusters are the densest stellar systems in the universe, with masses of ~ 107M⊙ and sizes of ~ 5pc. They are almost ubiquitous at the centres of nearby galaxies with masses similar to, or lower than the Milky Way. Their occurrence both in spirals and dwarf elliptical galaxies appears to be a strong function of total galaxy light or mass. Nucleation fractions are up to 100% for total galaxy magnitudes of M B = -19mag or total galaxy luminosities of about L B = 1010 L ⊙ and falling nucleation fractions for both smaller and higher galaxy masses. Although nuclear star clusters are so common, their formation mechanisms are still under debate. The two main formation scenarios proposed are the infall and subsequent merging of star clusters and the in-situ formation of stars at the center of a galaxy. Here, I review the state-of-the-art of nuclear star cluster observations concerning their structure, stellar populations and kinematics. These observations are used to constrain the proposed formation scenarios for nuclear star clusters. Constraints from observations show, that likely both cluster infall and in-situ star formation are at work. The relative importance of these two mechanisms is still subject of investigation.

  7. Combined Mapping of Multiple clUsteriNg ALgorithms (COMMUNAL): A Robust Method for Selection of Cluster Number, K.

    PubMed

    Sweeney, Timothy E; Chen, Albert C; Gevaert, Olivier

    2015-11-19

    In order to discover new subsets (clusters) of a data set, researchers often use algorithms that perform unsupervised clustering, namely, the algorithmic separation of a dataset into some number of distinct clusters. Deciding whether a particular separation (or number of clusters, K) is correct is a sort of 'dark art', with multiple techniques available for assessing the validity of unsupervised clustering algorithms. Here, we present a new technique for unsupervised clustering that uses multiple clustering algorithms, multiple validity metrics, and progressively bigger subsets of the data to produce an intuitive 3D map of cluster stability that can help determine the optimal number of clusters in a data set, a technique we call COmbined Mapping of Multiple clUsteriNg ALgorithms (COMMUNAL). COMMUNAL locally optimizes algorithms and validity measures for the data being used. We show its application to simulated data with a known K, and then apply this technique to several well-known cancer gene expression datasets, showing that COMMUNAL provides new insights into clustering behavior and stability in all tested cases. COMMUNAL is shown to be a useful tool for determining K in complex biological datasets, and is freely available as a package for R.

  8. Allodynia in Cluster Headache.

    PubMed

    Wilbrink, Leopoldine A; Louter, Mark A; Teernstra, Onno Pm; van Zwet, Erik W; Huygen, Frank Jpm; Haan, Joost; Ferrari, Michel D; Terwindt, Gisela M

    2017-03-04

    Cutaneous allodynia is an established marker for central sensitization in migraine. There is debate whether cutaneous allodynia may also occur in cluster headache, another episodic headache disorder. Here we examined the presence and severity of allodynia in a large well-defined nation-wide population of people with cluster headache.Using validated questionnaires we assessed, cross-sectionally, ictal allodynia and comorbid depression and migraine in the nation-wide "Leiden University Cluster headache neuro-Analysis" (LUCA) study. Participants with cluster headache were diagnosed according to the International Classification of Headache Disorders criteria. Multivariate regression models were used, with correction for demographic factors and cluster headache subtype (chronic vs. episodic; recent attacks < 1 month vs. no recent attacks).In total 606/798 (75.9%) participants with cluster headache responded of whom 218/606 (36%) had allodynia during attacks. Female gender (OR 2.05, 95% CI 1.28-3.29), low age at onset (OR 0.98, 95% CI 0.96- 0.99), lifetime depression (OR 1.63; 95% CI 1.06-2.50), comorbid migraine (OR 1.96; 95% CI 1.02-3.79), and having recent attacks (OR 1.80; 95% CI 1.13-2.86), but not duration of attacks and chronic cluster headache, were independent risk factors for allodynia.The high prevalence of cutaneous allodynia with similar risk factors for allodynia as found for migraine suggests that central sensitization, like in migraine, also occurs in cluster headache. In clinical practice, awareness that people with cluster headache may suffer from allodynia can in the future be an important feature in treatment options.

  9. Lipid Bilayers: Clusters, Domains and Phases

    PubMed Central

    Ackerman, David G.; Feigenson, Gerald W.

    2015-01-01

    In this chapter we discuss the complex mixing behavior of plasma membrane lipids. To do so, we first introduce the plasma membrane and membrane mixtures often used to model its complexity. We then discuss the nature of lipid phase behavior in bilayers and the distinction between these phases and other manifestations of nonrandom mixing found in one-phase mixtures, such as clusters, micelles, and microemulsions. Finally, we demonstrate the applicability of Gibbs phase diagrams to the study of increasingly complex model membrane systems, with a focus on phase coexistence, morphology and their implications for the cell plasma membrane. PMID:25658342

  10. Ground and Excited States of the [Fe(H₂O)₆]²⁺ and [Fe(H₂O)₆]³⁺ Clusters: Insight into the Electronic Structure of the [Fe(H₂O)₆]²⁺-[Fe(H₂O)₆]³⁺ Complex.

    PubMed

    Miliordos, Evangelos; Xantheas, Sotiris S

    2015-04-14

    We report the ground and low-lying electronically excited states of the [Fe(H2O)6](2+) and [Fe(H2O)6](3+) clusters using multiconfiguration electronic structure theory. In particular, we have constructed the potential energy curves (PECs) with respect to the iron-oxygen distance when removing all water ligands at the same time from the cluster minima and established their correlation to the long-range dissociation channels. Due to the fact that both the second and third ionization potentials of iron are larger than the one for water, the ground-state products asymptotically correlate with dissociation channels that are repulsive in nature at large separations, as they contain at least one H2O(+) fragment and a singly positively charged metal center (Fe(+)). The most stable equilibrium structures emanate, via intersections and/or avoided crossings, from the channels consisting of the lowest electronic states of Fe(2+)((5)D, 3d(6)) or Fe(3+)((6)S, 3d(5)) and six neutral water molecules. Upon hydration, the ground state of Fe(2+)(H2O)6 is a triply ((5)Tg) degenerate one, with the doubly ((5)Eg) degenerate state lying ∼20 kcal/mol higher in energy. Similarly, the Fe(3+)(H2O)6 cluster has a ground state of (6)Ag symmetry under Th symmetry, which is well-separated from the first excited state. We also examine a multitude of electronically excited states of many possible spin multiplicities and report the optimized geometries for several selected states. The PECs of those states exhibit a high density of states. Focusing on the ground and the first few excited states of the [Fe(H2O)6](2+) and [Fe(H2O)6](3+) clusters, we studied their mutual interaction in the gas phase. We obtained the optimal geometries of the Fe(2+)(H2O)6-Fe(3+)(H2O)6 gas-phase complex for different Fe-Fe distances. For distances shorter than 6.0 Å, the water molecules in the respective first solvation shells located between the two metal centers were found to interact via weak hydrogen bonds. We

  11. Structural Changes Correlated with Magnetic Spin State Isomorphism in the S2 State of the Mn4CaO5 Cluster in the Oxygen-Evolving Complex of Photosystem II.

    PubMed

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D; Garachtchenko, Anna; Young, Iris; Weng, Tsu-Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K; Yano, Junko

    2016-08-01

    The Mn4CaO5 cluster in Photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. Such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.

  12. Structural changes correlated with magnetic spin state isomorphism in the S2 state of the Mn4CaO5 cluster in the oxygen-evolving complex of photosystem II

    SciTech Connect

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D.; Garachtchenko, Anna; Young, Iris D.; Weng, Tsu -Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K.; Yano, Junko

    2016-05-09

    The Mn4CaO5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.

  13. Structural changes correlated with magnetic spin state isomorphism in the S2 state of the Mn4CaO5 cluster in the oxygen-evolving complex of photosystem II

    DOE PAGES

    Chatterjee, Ruchira; Han, Guangye; Kern, Jan; ...

    2016-05-09

    The Mn4CaO5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, withmore » a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.« less

  14. Extending Beowulf Clusters

    USGS Publications Warehouse

    Steinwand, Daniel R.; Maddox, Brian; Beckmann, Tim; Hamer, George

    2003-01-01

    Beowulf clusters can provide a cost-effective way to compute numerical models and process large amounts of remote sensing image data. Usually a Beowulf cluster is designed to accomplish a specific set of processing goals, and processing is very efficient when the problem remains inside the constraints of the original design. There are cases, however, when one might wish to compute a problem that is beyond the capacity of the local Beowulf system. In these cases, spreading the problem to multiple clusters or to other machines on the network may provide a cost-effective solution.

  15. Dwarfs in Coma Cluster

    NASA Technical Reports Server (NTRS)

    2007-01-01

    [figure removed for brevity, see original site] Click on image for larger poster version

    This false-color mosaic of the central region of the Coma cluster combines infrared and visible-light images to reveal thousands of faint objects (green). Follow-up observations showed that many of these objects, which appear here as faint green smudges, are dwarf galaxies belonging to the cluster. Two large elliptical galaxies, NGC 4889 and NGC 4874, dominate the cluster's center. The mosaic combines visible-light data from the Sloan Digital Sky Survey (color coded blue) with long- and short-wavelength infrared views (red and green, respectively) from NASA's Spitzer Space Telescope.

  16. Magnetization of ferromagnetic clusters

    SciTech Connect

    Onishi, Naoki; Bertsch, G.; Yabana, Kazuhiro

    1995-02-01

    The magnetization and deflection profiles of magnetic clusters in a Stern-Gerlach magnet are calculated for conditions under which the magnetic moment is fixed in the intrinsic frame of the cluster, and the clusters enter the magnetic field adiabatically. The predicted magnetization is monotonic in the Langevin parameter, the ratio of magnetic energy {mu}{sub 0}B to thermal energy k{sub B}T. In low field the average magnetization is 2/3 of the Langevin function. The high-field moment approaches saturation asymptotically as B{sup {minus}1/2} instead of the B{sup {minus}1} dependence in the Langevin function.

  17. H-cluster stars

    NASA Astrophysics Data System (ADS)

    Lai, X. Y.; Gao, C. Y.; Xu, R. X.

    2013-06-01

    The study of dense matter at ultrahigh density has a very long history, which is meaningful for us to understand not only cosmic events in extreme circumstances but also fundamental laws of physics. It is well known that the state of cold matter at supranuclear density depends on the non-perturbative nature of quantum chromodynamics (QCD) and is essential for modelling pulsars. A so-called H-cluster matter is proposed in this paper as the nature of dense matter in reality. In compact stars at only a few nuclear densities but low temperature, quarks could be interacting strongly with each other there. That might render quarks grouped in clusters, although the hypothetical quark clusters in cold dense matter have not been confirmed due to the lack of both theoretical and experimental evidence. Motivated by recent lattice QCD simulations of the H-dibaryons (with structure uuddss), we therefore consider here a possible kind of quark clusters, H-clusters, that could emerge inside compact stars during their initial cooling as the dominant components inside (the degree of freedom could then be H-clusters there). Taking into account the in-medium stiffening effect, we find that at baryon densities of compact stars H-cluster matter could be more stable than nuclear matter. We also find that for the H-cluster matter with lattice structure, the equation of state could be so stiff that it would seem to be `superluminal' in the most dense region. However, the real sound speed for H-cluster matter is in fact difficult to calculate, so at this stage we do not put constraints on our model from the usual requirement of causality. We study the stars composed of H-clusters, i.e. H-cluster stars, and derive the dependence of their maximum mass on the in-medium stiffening effect, showing that the maximum mass could be well above 2 M⊙ as observed and that the resultant mass-radius relation fits the measurement of the rapid burster under reasonable parameters. Besides a general

  18. 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.

  19. 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

  20. Emergence of clustering: Role of inhibition

    NASA Astrophysics Data System (ADS)

    Dwivedi, Sanjiv K.; Jalan, Sarika

    2014-09-01

    Though biological and artificial complex systems having inhibitory connections exhibit a high degree of clustering in their interaction pattern, the evolutionary origin of clustering in such systems remains a challenging problem. Using genetic algorithm we demonstrate that inhibition is required in the evolution of clique structure from primary random architecture, in which the fitness function is assigned based on the largest eigenvalue. Further, the distribution of triads over nodes of the network evolved from mixed connections reveals a negative correlation with its degree providing insight into origin of this trend observed in real networks.

  1. Challenges in imaging cell surface receptor clusters

    NASA Astrophysics Data System (ADS)

    Medda, Rebecca; Giske, Arnold; Cavalcanti-Adam, Elisabetta Ada

    2016-01-01

    Super-resolution microscopy offers unique tools for visualizing and resolving cellular structures at the molecular level. STED microscopy is a purely optical method where neither complex sample preparation nor mathematical post-processing is required. Here we present the use of STED microscopy for imaging receptor cluster composition. We use two-color STED to further determine the distribution of two different receptor subunits of the family of receptor serine/threonine kinases in the presence or absence of their ligands. The implications of receptor clustering on the downstream signaling are discussed, and future challenges are also presented.

  2. Prokaryotic Gene Clusters: A Rich Toolbox for Synthetic Biology

    PubMed Central

    Fischbach, Michael; Voigt, Christopher A.

    2014-01-01

    Bacteria construct elaborate nanostructures, obtain nutrients and energy from diverse sources, synthesize complex molecules, and implement signal processing to react to their environment. These complex phenotypes require the coordinated action of multiple genes, which are often encoded in a contiguous region of the genome, referred to as a gene cluster. Gene clusters sometimes contain all of the genes necessary and sufficient for a particular function. As an evolutionary mechanism, gene clusters facilitate the horizontal transfer of the complete function between species. Here, we review recent work on a number of clusters whose functions are relevant to biotechnology. Engineering these clusters has been hindered by their regulatory complexity, the need to balance the expression of many genes, and a lack of tools to design and manipulate DNA at this scale. Advances in synthetic biology will enable the large-scale bottom-up engineering of the clusters to optimize their functions, wake up cryptic clusters, or to transfer them between organisms. Understanding and manipulating gene clusters will move towards an era of genome engineering, where multiple functions can be “mixed-and-matched” to create a designer organism. PMID:21154668

  3. Combining cluster number counts and galaxy clustering

    NASA Astrophysics Data System (ADS)

    Lacasa, Fabien; Rosenfeld, Rogerio

    2016-08-01

    The abundance of clusters and the clustering of galaxies are two of the important cosmological probes for current and future large scale surveys of galaxies, such as the Dark Energy Survey. In order to combine them one has to account for the fact that they are not independent quantities, since they probe the same density field. It is important to develop a good understanding of their correlation in order to extract parameter constraints. We present a detailed modelling of the joint covariance matrix between cluster number counts and the galaxy angular power spectrum. We employ the framework of the halo model complemented by a Halo Occupation Distribution model (HOD). We demonstrate the importance of accounting for non-Gaussianity to produce accurate covariance predictions. Indeed, we show that the non-Gaussian covariance becomes dominant at small scales, low redshifts or high cluster masses. We discuss in particular the case of the super-sample covariance (SSC), including the effects of galaxy shot-noise, halo second order bias and non-local bias. We demonstrate that the SSC obeys mathematical inequalities and positivity. Using the joint covariance matrix and a Fisher matrix methodology, we examine the prospects of combining these two probes to constrain cosmological and HOD parameters. We find that the combination indeed results in noticeably better constraints, with improvements of order 20% on cosmological parameters compared to the best single probe, and even greater improvement on HOD parameters, with reduction of error bars by a factor 1.4-4.8. This happens in particular because the cross-covariance introduces a synergy between the probes on small scales. We conclude that accounting for non-Gaussian effects is required for the joint analysis of these observables in galaxy surveys.

  4. Methylidene rare-earth-metal complex mediated transformations of C=N, N=N and N-H bonds: new routes to imido rare-earth-metal clusters.

    PubMed

    Hong, Jianquan; Zhang, Lixin; Wang, Kai; Zhang, Yin; Weng, Linhong; Zhou, Xigeng

    2013-06-10

    Three new patterns of reactivity of rare-earth metal methylidene complexes have been established and thus have resulted in access to a wide variety of imido rare-earth metal complexes [L3Ln3(μ2-Me)3(μ3-Me)(μ-NR)] (L = [PhC(NC6H3iPr2-2,6)2](-); R = Ph, Ln = Y (2 a), Lu (2 b); R = 2,6-Me2C6H3, Ln = Y (3 a), Lu (3 b); R = p-ClC6H4, Ln = Y (4 a), Lu (4 b); R = p-MeOC6H4, Ln = Y (5 a), Lu (5 b); R = Me2CHCH2CH2, Ln = Y (6 a), Lu (6 b)) and [{L3Lu3(μ2-Me)3(μ3-Me)}2(μ-NR'N)] (R' = (CH2)6 (7 b), (C6H4)2 (8 b)). Complex 2 b was treated with an excess of CO2 to give the corresponding carboxylate complex [L3Lu3(μ-η(1):η(1)-O2CCH3)3(μ-η(1):η(2)-O2C-CH3)(μ-η(1):η(1):η(2)-O2CNPh)] (9 b) easily. Complex 2 a could undergo the selective μ3-Me abstraction reaction with phenyl acetylene to give the mixed imido/alkynide complex [L3Y3(μ2-Me)3(μ3-η(1):η(1):η(3)-NPh)(μ3-C≡CPh)] (10 a) in high yield. Treatment of 2 with one equivalent of thiophenol gave the selective μ3-methyl-abstracted products [L3Ln3(μ2-Me)3(μ3-η(1):η(1):η(3)-NPh)(μ3-SPh)] (Ln = Y (11 a); Lu (11 b). All new complexes have been characterized by elemental analysis, NMR spectroscopy, and most of the structures confirmed by X-ray diffraction.

  5. Coevolutionary dynamics with clustering behaviors on cyclic competition

    NASA Astrophysics Data System (ADS)

    Dong, Linrong; Yang, Guangcan

    2012-05-01

    We propose a dynamic model for describing clustering behaviors on a cyclic game, in which the same species form a cluster to compete. The rates of consuming the prey depend not only on the individual competing ability v, but also on the two interacting cluster’s sizes. The fragmentation and coagulation rates of the clusters are related to the cohesive strength among the individuals. A new parameter u is introduced to indicate the uniting degree. We find that the probability distribution of the clustering sizes is almost a power law in a large regime specified by the two parameters, which reflects the scale-free behavior in complex systems. In addition, the exponential magnitudes are mostly in the range of real social systems. Our simulation shows that clustering promotes biodiversity. At steady state, the amounts about the three species evolve tempestuously with asymmetric period; the aggregations about big size’s clusters to compete are obvious and on-off intermittence.

  6. Structures and Components in Galaxy Clusters: Observations and Models

    NASA Astrophysics Data System (ADS)

    Bykov, A. M.; Churazov, E. M.; Ferrari, C.; Forman, W. R.; Kaastra, J. S.; Klein, U.; Markevitch, M.; de Plaa, J.

    2015-05-01

    Clusters of galaxies are the largest gravitationally bounded structures in the Universe dominated by dark matter. We review the observational appearance and physical models of plasma structures in clusters of galaxies. Bubbles of relativistic plasma which are inflated by supermassive black holes of AGNs, cooling and heating of the gas, large scale plasma shocks, cold fronts, non-thermal halos and relics are observed in clusters. These constituents are reflecting both the formation history and the dynamical properties of clusters of galaxies. We discuss X-ray spectroscopy as a tool to study the metal enrichment in clusters and fine spectroscopy of Fe X-ray lines as a powerful diagnostics of both the turbulent plasma motions and the energetics of the non-thermal electron populations. The knowledge of the complex dynamical and feedback processes is necessary to understand the energy and matter balance as well as to constrain the role of the non-thermal components of clusters.

  7. How Clusters Work

    EPA Pesticide Factsheets

    Technology innovation clusters are geographic concentrations of interconnected companies, universities, and other organizations with a focus on environmental technology. They play a key role in addressing the nation’s pressing environmental problems.

  8. [Treatment of cluster headache].

    PubMed

    Fabre, N

    2005-07-01

    Remarkable therapeutic improvements have come forward recently for trigemino-autonomic cephalalgias. Attack treatment in cluster headache is based on sumatriptan and oxygen. Non-vasoconstrictive treatments are opening a new post-triptan era but are not yet applicable. Prophylactic treatment of cluster headache is based on verapamil and lithium. The efficacy of anti-epileptic drugs in cluster headache remains to be demonstrated. Surgical treatment aimed at the parasympathetic pathways and at the trigeminal nerve demonstrates a high rate of recurrence and adverse events and questions about the relevance of a "peripheral" target in cluster headache. The efficacy of continuous hypothalamic stimulation in patients with intractable headache constitutes a breakthrough, but must be demonstrated at a larger scale and the benefice/risk ratio must be carefully evaluated. Indomethacin still remains the gold standard in paroxysmal hemicrania treatment. Until recently SUNCT was considered an intractable condition. However there are some reports of complete relief with lamotrigine, topiramate and gabapentin.

  9. Clustered frequency comb.

    PubMed

    Matsko, Andrey B; Savchenkov, Anatoliy A; Huang, Shu-Wei; Maleki, Lute

    2016-11-01

    We show theoretically that it is feasible to generate a spectrally broad Kerr frequency comb consisting of several spectral clusters phase matched due to interplay among second- and higher-order group velocity dispersion contributions. We validate the theoretical analysis experimentally by driving a magnesium fluoride resonator, characterized with 110 GHz free spectral range, with a continuous wave light at 1.55 μm and observing two comb clusters separated by nearly two-thirds of an octave.

  10. Cluster State Quantum Computing

    DTIC Science & Technology

    2012-12-01

    implementation of quantum computation,” Fortschr. Phys. 48, 771 (2000). [Dragoman01] D. Dragoman, “Proposal for a three-qubit teleportation experiment”, Phys...CLUSTER STATE QUANTUM COMPUTING DECEMBER 2012 INTERIM TECHNICAL REPORT APPROVED FOR PUBLIC RELEASE; DISTRIBUTION...From - To) NOV 2010 – OCT 2012 4. TITLE AND SUBTITLE CLUSTER STATE QUANTUM COMPUTING 5a. CONTRACT NUMBER IN-HOUSE 5b. GRANT NUMBER N/A 5c

  11. Globular clusters with Gaia

    NASA Astrophysics Data System (ADS)

    Pancino, E.; Bellazzini, M.; Giuffrida, G.; Marinoni, S.

    2017-01-01

    The treatment of crowded fields in Gaia data will only be a reality in a few years from now. In particular, for globular clusters, only the end-of-mission data (public in 2022-2023) will have the necessary full crowding treatment and will reach sufficient quality for the faintest stars. As a consequence, the work on the deblending and decontamination pipelines is still ongoing. We describe the present status of the pipelines for different Gaia instruments, and we model the end-of-mission crowding errors on the basis of available information. We then apply the nominal post-launch Gaia performances, appropriately worsened by the estimated crowding errors, to a set of 18 simulated globular clusters with different concentration, distance, and field contamination. We conclude that there will be 103-104 stars with astrometric performances virtually untouched by crowding (contaminated by <1 mmag) in the majoritiy of clusters. The most limiting factor will be field crowding, not cluster crowding: the most contaminated clusters will only contain 10-100 clean stars. We also conclude that: (i) the systemic proper motions and parallaxes will be determined to 1% or better up to ≃15 kpc, and the nearby clusters will have radial velocities to a few km s-1 ; (ii) internal kinematics will be of unprecendented quality, cluster masses will be determined to ≃10% up to 15 kpc and beyond, and it will be possible to identify differences of a few km s-1 or less in the kinematics (if any) of cluster sub-populations up to 10 kpc and beyond; (iii) the brightest stars (V≃17 mag) will have space-quality, wide-field photometry (mmag errors), and all Gaia photometry will have 1-3% errors on the absolute photometric calibration.

  12. Chemistry within Molecular Clusters

    DTIC Science & Technology

    1992-05-29

    molecule reaction of the fragment cations with a neutral DME within the bulk cluster, to form a trimethyloxonium cation intermediate. Similar ion...trimethyloxonium intermediate as the common intermediate for the observed products. We therefore speculate that the DME cluster reactions leading to the same...1982, 20, 51, Ibid. Kinetics of Ion-Molecule Reactions ; Ausloos, P., Ed.; Plenum, New York, 1979; p. 69. (18) Ono, Y.; Ng, C. Y. J. Am. Chem. Soc. 1982

  13. Wild Duck Cluster

    NASA Technical Reports Server (NTRS)

    2005-01-01

    On April 7, 2005, the Deep Impact spacecraft's Impactor Target Sensor camera recorded this image of M11, the Wild Duck cluster, a galactic open cluster located 6 thousand light years away. The camera is located on the impactor spacecraft, which will image comet Tempel 1 beginning 22 hours before impact until about 2 seconds before impact. Impact with comet Tempel 1 is planned for July 4, 2005.

  14. Parallel Wolff Cluster Algorithms

    NASA Astrophysics Data System (ADS)

    Bae, S.; Ko, S. H.; Coddington, P. D.

    The Wolff single-cluster algorithm is the most efficient method known for Monte Carlo simulation of many spin models. Due to the irregular size, shape and position of the Wolff clusters, this method does not easily lend itself to efficient parallel implementation, so that simulations using this method have thus far been confined to workstations and vector machines. Here we present two parallel implementations of this algorithm, and show that one gives fairly good performance on a MIMD parallel computer.

  15. Cluster functional renormalization group

    NASA Astrophysics Data System (ADS)

    Reuther, Johannes; Thomale, Ronny

    2014-01-01

    Functional renormalization group (FRG) has become a diverse and powerful tool to derive effective low-energy scattering vertices of interacting many-body systems. Starting from a free expansion point of the action, the flow of the RG parameter Λ allows us to trace the evolution of the effective one- and two-particle vertices towards low energies by taking into account the vertex corrections between all parquet channels in an unbiased fashion. In this work, we generalize the expansion point at which the diagrammatic resummation procedure is initiated from a free UV limit to a cluster product state. We formulate a cluster FRG scheme where the noninteracting building blocks (i.e., decoupled spin clusters) are treated exactly, and the intercluster couplings are addressed via RG. As a benchmark study, we apply our cluster FRG scheme to the spin-1/2 bilayer Heisenberg model (BHM) on a square lattice where the neighboring sites in the two layers form the individual two-site clusters. Comparing with existing numerical evidence for the BHM, we obtain reasonable findings for the spin susceptibility, the spin-triplet excitation energy, and quasiparticle weight even in coupling regimes close to antiferromagnetic order. The concept of cluster FRG promises applications to a large class of interacting electron systems.

  16. Cluster synthesis. 39. New platinum-ruthenium carbonyl cluster complexes with bridging hydride ligands. Synthesis and structural characterizations of Ru sub 4 Pt(CO) sub 13 (COD)(. mu. -H) sub 2 , Ru sub 3 Pt(CO) sub 9 (. mu. -CO)(COD)(. mu. -H) sub 2 , Ru sub 4 Pt sub 2 (CO) sub 11 (COD) sub 2 (. mu. sub 3 -H) sub 2 , and Ru sub 5 Pt sub 5 (CO) sub 18 (COD) sub 2 (. mu. -H) sub 2 , COD = Cycloocta-1,5-diene

    SciTech Connect

    Adams, R.D.; Zhaoyang Li; Jauching Lii; Wengan Wu )

    1992-08-05

    The reaction of Ru{sub 4}(CO){sub 13}({mu}-H){sub 2} (1) with Pt(COD){sub 2} at 25 C yielded four new platinum-ruthenium carbonyl cluster complexes Ru{sub 4}Pt(CO){sub 13}(COD)({mu}-H){sub 2} (2) (37%), Ru{sub 3}Pt(CO){sub 9}({mu}-CO)(COD)({mu}-H){sub 2} (3) (10%), Ru{sub 4}Pt{sub 2}-(CO){sub 11}(COD){sub 2}({mu}{sub 3}-H){sub 2} (4) (2.5%), and Ru{sub 5}Pt{sub 5}(CO){sub 18}(COD){sub 2}({mu}{sub 3}-H){sub 2} (5) (1%). All compounds were characterized by IR, {sup 1}H NMR, and single-crystal X-ray diffraction analyses. The cluster of compound 2 consists of a butterfly tetrahedron of four ruthenium atoms with one triangular face capped by a Pt(COD) grouping. Compound 3 consists of a cluster of three ruthenium atoms and one platinum atom in a tetrahedral arrangement. Compound 4 consists of a tetrahedral cluster of four ruthenium atoms with two of the triangular faces capped by Pt(COD) groupings. The other two triangular faces have triply bridging hydride ligands. In the cluster of compound 5, the five ruthenium and four of the platinum atoms are arranged in the form of a face-shared bioctahedron. The shared face consists of three of the platinum atoms. The fifth platinum atom is a cap on one of the Ru{sub 2}Pt triangles. Two hydride ligands are believed to bridge metals of the triangular faces on the opposite ends of the bioctahedron.

  17. Theory-driven group-based complex intervention to support self-management of osteoarthritis and low back pain in primary care physiotherapy: protocol for a cluster randomised controlled feasibility trial (SOLAS)

    PubMed Central

    Hurley, Deirdre A; Hall, Amanda M; Currie-Murphy, Laura; Pincus, Tamar; Kamper, Steve; Maher, Chris; McDonough, Suzanne M; Lonsdale, Chris; Walsh, Nicola E; Guerin, Suzanne; Segurado, Ricardo; Matthews, James

    2016-01-01

    Introduction International clinical guidelines consistently endorse the promotion of self-management (SM), including physical activity for patients with chronic low back pain (CLBP) and osteoarthritis (OA). Patients frequently receive individual treatment and advice to self-manage from physiotherapists in primary care, but the successful implementation of a clinical and cost-effective group SM programme is a key priority for health service managers in Ireland to maximise long-term outcomes and efficient use of limited and costly resources. Methods/analysis This protocol describes an assessor-blinded cluster randomised controlled feasibility trial of a group-based education and exercise intervention underpinned by self-determination theory designed to support an increase in SM behaviour in patients with CLBP and OA in primary care physiotherapy. The primary care clinic will be the unit of randomisation (cluster), with each clinic randomised to 1 of 2 groups providing the Self-management of Osteoarthritis and Low back pain through Activity and Skills (SOLAS) intervention or usual individual physiotherapy. Patients are followed up at 6 weeks, 2 and 6 months. The primary outcomes are the (1) acceptability and demand of the intervention to patients and physiotherapists, (2) feasibility and optimal study design/procedures and sample size for a definitive trial. Secondary outcomes include exploratory analyses of: point estimates, 95% CIs, change scores and effect sizes in physical function, pain and disability outcomes; process of change in target SM behaviours and selected mediators; and the cost of the intervention to inform a definitive trial. Ethics/dissemination This feasibility trial protocol was approved by the UCD Human Research Ethics—Sciences Committee (LS-13-54 Currie-Hurley) and research access has been granted by the Health Services Executive Primary Care Research Committee in January 2014. The study findings will be disseminated to the research

  18. Migration Mechanisms of Oxygen Interstitial Clusters in UO2

    SciTech Connect

    Xian-Ming Bai; Anter El-Azab; Jianguo Yu; Todd R. Allen

    2013-01-01

    Understanding the migration kinetics of radiation-induced point defects and defect clusters is a key to predicting the microstructural evolution and mass transport in nuclear fuels. Although the diffusion kinetics of point defects in UO2 is well explored both experimentally and theoretically, the kinetics of defect clusters is not well understood. In this work the migration mechanisms of oxygen interstitial clusters of size one to five atoms (1Oi – 5Oi) in UO2 are investigated by temperature-accelerated dynamics simulations without any a priori assumptions of migration mechanisms. It is found that the migration paths of oxygen interstitial clusters are complex and non-intuitive and that multiple migration paths and barriers exist for some clusters. It is also found that the cluster migration barrier does not increase with increasing cluster size and its magnitude has the following order: 2Oi < 3Oi < 1Oi < 5Oi < 4Oi. Possible finite-size effects are checked with three different sized systems. The results show good agreement with other available experimental and theoretical data. In particular, the relatively large migration barriers of cuboctahedral clusters (4Oi and 5Oi) are in good agreement with the experimentally measured oxygen diffusion activation energy in U4O9, which is thought to contain many such clusters. The cluster migration sequence may explain the interesting relationship between the oxygen diffusivity and stoichiometry in UO2+x.

  19. Synthesis, structural characterization, and antiinflammatory activity of triethylphosphinegold(I) sulfanylpropenoates of the type [(AuPEt3)2xspa] [H2xspa = 3-(aryl)-2-sulfanylpropenoic acid]: an (H2O)6 cluster in the lattice of the complexes [(AuPEt3)2xspa] x 3 H2O.

    PubMed

    Barreiro, Elena; Casas, José S; Couce, María D; Gato, Angeles; Sánchez, Agustín; Sordo, José; Varela, José M; Vázquez López, Ezequiel M

    2008-07-21

    Gold complexes of the type [(AuPEt3)2xspa] were prepared by reacting AuPEt3Cl in basic media with the 3-(aryl)-2-sulfanylpropenoic acids H2xspa [x = p, Clp, -o-mp, -p-mp, -o-hp, -p-hp, diBr-o-hp, f, t, -o-py; p = 3-phenyl, Clp = 3-(2-chlorophenyl)-, -o-mp = 3-(2-methoxyphenyl)-, -p-mp = 3-(4-methoxyphenyl)-, -o-hp = 3-(2-hydroxyphenyl)-, -p-hp = 3-(4-hydroxyphenyl)-, diBr-o-hp = 3-(3,5- dibromo-2-hydroxyphenyl)-, f = 3-(2-furyl)-, t = 3-(2-thienyl)-, -o-py = 3-(2-pyridyl); spa = 2-sulfanylpropenoato], and 2-cyclopentylidene-2-sulfanylacetic acid (H2cpa). The complexes were characterized by spectroscopic methods (IR, (1)H, (13)C and (31)P NMR) and mass spectrometry, and the complexes [(AuPEt3)2pspa] x 3 H2O, [(AuPEt3)2-p-hpspa] x 3 H2O, [(AuPEt3)2tspa)] x 3 H2O, and [(AuPEt3)2-o-hpspa] by X-ray diffractometry. The crystals of the first three complexes contain (H2O)6 clusters hydrogen bonded to [(AuPEt3)2xspa]2 dimer units, whereas in the -o-hpspa derivative the hydrogen bonds are between the monomer [(AuPEt3)2-o-hpspa] units. The antiinflammatory activity of the complexes against plantar edema induced by carrageenan in rats is generally significant, with the values for the o-hpspa and tspa derivatives being particularly high.

  20. Hot outflows in galaxy clusters

    NASA Astrophysics Data System (ADS)

    Kirkpatrick, C. C.; McNamara, B. R.

    2015-10-01

    The gas-phase metallicity distribution has been analysed for the hot atmospheres of 29 galaxy clusters using Chandra X-ray Observatory observations. All host brightest cluster galaxies (BCGs) with X-ray cavity systems produced by radio AGN. We find high elemental abundances projected preferentially along the cavities of 16 clusters. The metal-rich plasma was apparently lifted out of the BCGs with the rising X-ray cavities (bubbles) to altitudes between twenty and several hundred kiloparsecs. A relationship between the maximum projected altitude of the uplifted gas (the `iron radius') and jet power is found with the form R_Fe ∝ P_jet^{0.45}. The estimated outflow rates are typically tens of solar masses per year but exceed 100 M⊙ yr- 1 in the most powerful AGN. The outflow rates are 10-20 per cent of the cooling rates, and thus alone are unable to offset a cooling inflow. Nevertheless, hot outflows effectively redistribute the cooling gas and may play a significant role at regulating star formation and AGN activity in BCGs and presumably in giant elliptical galaxies. The metallicity distribution overall can be complex, perhaps due to metal-rich gas returning in circulation flows or being blown around in the hot atmospheres. Roughly 15 per cent of the work done by the cavities is expended lifting the metal-enriched gas, implying their nuclear black holes have increased in mass by at least ˜107-109 M⊙. Finally, we show that hot outflows can account for the broad, gas-phase metallicity distribution compared to the stellar light profiles of BCGs, and we consider a possible connection between hot outflows and cold molecular gas flows discovered in recent Atacama Large Millimeter Array observations.

  1. Towards Semantically Sensitive Text Clustering: A Feature Space Modeling Technology Based on Dimension Extension

    PubMed Central

    Liu, Yuanchao; Liu, Ming; Wang, Xin

    2015-01-01

    The objective of text clustering is to divide document collections into clusters based on the similarity between documents. In this paper, an extension-based feature modeling approach towards semantically sensitive text clustering is proposed along with the corresponding feature space construction and similarity computation method. By combining the similarity in traditional feature space and that in extension space, the adverse effects of the complexity and diversity of natural language can be addressed and clustering semantic sensitivity can be improved correspondingly. The generated clusters can be organized using different granularities. The experimental evaluations on well-known clustering algorithms and datasets have verified the effectiveness of our approach. PMID:25794172

  2. Towards semantically sensitive text clustering: a feature space modeling technology based on dimension extension.

    PubMed

    Liu, Yuanchao; Liu, Ming; Wang, Xin

    2015-01-01

    The objective of text clustering is to divide document collections into clusters based on the similarity between documents. In this paper, an extension-based feature modeling approach towards semantically sensitive text clustering is proposed along with the corresponding feature space construction and similarity computation method. By combining the similarity in traditional feature space and that in extension space, the adverse effects of the complexity and diversity of natural language can be addressed and clustering semantic sensitivity can be improved correspondingly. The generated clusters can be organized using different granularities. The experimental evaluations on well-known clustering algorithms and datasets have verified the effectiveness of our approach.

  3. Behavioral Clustering of School Children.

    ERIC Educational Resources Information Center

    Huberty, Carl J.; DiStefano, Christine; Kamphaus, Randy W.

    1997-01-01

    How a cluster analysis is conducted, validated, and interpreted is illustrated using a 14-scale behavioral assessment instrument and a national sample of 1,228 elementary school students. Method, cluster typology, validity, cluster structure, and prediction of cluster membership are discussed. (Author/SLD)

  4. Formation and growth of molecular clusters containing sulfuric acid, water, ammonia, and dimethylamine.

    PubMed

    DePalma, Joseph W; Doren, Douglas J; Johnston, Murray V

    2014-07-24

    The structures and thermochemistry of molecular clusters containing sulfuric acid, water, ammonia, and/or dimethylamine ((CH3)2NH or DMA) are explored using a combination of Monte Carlo configuration sampling, semiempirical calculations, and density functional theory (DFT) calculations. Clusters are of the general form [(BH(+))n(HSO4(-))n(H2O)y], where B = NH3 or DMA, 2 ≤ n ≤ 8, and 0 ≤ y ≤ 10. Cluster formulas are written based on the computed structures, which uniformly show proton transfer from each sulfuric acid molecule to a base molecule while the water molecules remain un-ionized. Cluster formation is energetically favorable, owing to strong electrostatic attraction among the ions. Water has a minor effect on the energetics of cluster formation, lowering the free energy of formation by ∼ 10% depending on the cluster size and number of water molecules. Cluster growth (addition of one base molecule and one sulfuric acid molecule to a pre-existing cluster) and base substitution (substituting DMA for ammonia) are also energetically favorable processes for both anhydrous and hydrated clusters. However, the effect of water is different for different bases. Hydrated ammonium bisulfate clusters have a more favorable free energy for growth (i.e., incrementing n with fixed y) than anhydrous clusters, while the reverse is observed for dimethylammonium bisulfate clusters, where the free energy for growth is more favorable for anhydrous clusters. The substitution of DMA for ammonia in bisulfate clusters is favorable but exhibits a complex water dependence. Base substitution in smaller bisulfate clusters is enhanced by the presence of water, while base substitution in larger bisulfate clusters is less favorable for hydrated clusters than that for anhydrous clusters. While DMA substitution can stabilize small clusters containing one or a few sulfuric acid molecules, the free energy advantage of forming amine clusters relative to ammonia clusters becomes less

  5. Clustered data in sports research.

    PubMed

    Hayen, A

    2006-05-01

    Clustered, or dependent, data, arise commonly in sports medicine and sports science research, particularly in studies of sports injury and biomechanics, particularly in sports injury trials that are randomised at team or club level, in cross-sectional surveys in which groups of individuals are studied and in studies with repeated measures designs. Clustering, or positive correlation among responses, arises because responses and outcomes from the same cluster will usually be more similar than from different clusters. Study designs with clustering will usually required an increased sample size when compared to those without clustering. Ignoring clustering in statistical analyses can also lead to misleading conclusions, including incorrect confidence intervals and p-values. Appropriate statistical analyses for clustered data must be adopted. This paper gives some examples of clustered data and discusses the implications of clustering on the design and analysis of studies in sports medicine and sports science research.

  6. Peeking Network States with Clustered Patterns

    SciTech Connect

    Kim, Jinoh; Sim, Alex

    2015-10-20

    Network traffic monitoring has long been a core element for effec- tive network management and security. However, it is still a chal- lenging task with a high degree of complexity for comprehensive analysis when considering multiple variables and ever-increasing traffic volumes to monitor. For example, one of the widely con- sidered approaches is to scrutinize probabilistic distributions, but it poses a scalability concern and multivariate analysis is not gen- erally supported due to the exponential increase of the complexity. In this work, we propose a novel method for network traffic moni- toring based on clustering, one of the powerful deep-learning tech- niques. We show that the new approach enables us to recognize clustered results as patterns representing the network states, which can then be utilized to evaluate “similarity” of network states over time. In addition, we define a new quantitative measure for the similarity between two compared network states observed in dif- ferent time windows, as a supportive means for intuitive analysis. Finally, we demonstrate the clustering-based network monitoring with public traffic traces, and show that the proposed approach us- ing the clustering method has a great opportunity for feasible, cost- effective network monitoring.

  7. Dust in galaxy clusters

    NASA Astrophysics Data System (ADS)

    Polikarpova, O. L.; Shchekinov, Yu. A.

    2017-02-01

    The conditions for the destruction of dust in hot gas in galaxy clusters are investigated. It is argued that extinction measurements can be subject to selection effects, hindering their use in obtaining trustworthy estimates of dust masses in clusters. It is shown, in particular, that the ratio of the dust mass to the extinction M d / S d increases as dust grains are disrupted, due to the rapid destruction of small grains. Over long times, this ratio can asymptotically reach values a factor of three higher than the mean value in the interstellar medium in the Galaxy. This lowers dust-mass estimates based on measurements of extinction in galaxy clusters. The characteristic lifetime of dust in hot cluster gas is determined by its possible thermal isolation by the denser medium of gas fragments within which the dust is ejected from galaxies, and can reach 100-300 million years, depending on the kinematics and morphology of the fragments. As a result, the mass fraction of dust in hot cluster gas can reach 1-3% of the Galactic value. Over its lifetime, dust can also be manifest through its far-infrared emission. The emission characteristics of the dust change as it is disrupted, and the ratio of the fluxes at 350 and 850 μm can increase appreciably. This can potentially serve as an indicator of the state of the dust and ambient gas.

  8. Spatio-temporal clustering

    NASA Astrophysics Data System (ADS)

    Kisilevich, Slava; Mansmann, Florian; Nanni, Mirco; Rinzivillo, Salvatore

    Spatio-temporal clustering is a process of grouping objects based on their spatial and temporal similarity. It is relatively new subfield of data mining which gained high popularity especially in geographic information sciences due to the pervasiveness of all kinds of location-based or environmental devices that record position, time or/and environmental properties of an object or set of objects in real-time. As a consequence, different types and large amounts of spatio-temporal data became available that introduce new challenges to data analysis and require novel approaches to knowledge discovery. In this chapter we concentrate on the spatio-temporal clustering in geographic space. First, we provide a classification of different types of spatio-temporal data. Then, we focus on one type of spatio-temporal clustering - trajectory clustering, provide an overview of the state-of-the-art approaches and methods of spatio-temporal clustering and finally present several scenarios in different application domains such as movement, cellular networks and environmental studies.

  9. Dithiolate complexes of manganese and rhenium: X-ray structure and properties of an unusual mixed valence cluster Mn3(CO)6(mu-eta2-SCH2CH2CH2S)3.

    PubMed

    Begum, Noorjahan; Hyder, Md Iqbal; Kabir, Shariff E; Hossain, G M Golzar; Nordlander, Ebbe; Rokhsana, Dalia; Rosenberg, Edward

    2005-12-26

    Treatment of Mn(2)(CO)(10) with 3,4-toluenedithiol and 1,2-ethanedithiol in the presence of Me(3)NO.2H(2)O in CH(2)Cl(2) at room temperature afforded the dinuclear complexes Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (1), and Mn(2)(CO)(6)(mu-eta(4)-SCH(2)CH(2)S-SCH(2)CH(2)S) (2), respectively. Similar reactions of Re(2)(CO)(10) with 3,4-toluenedithiol, 1,2-benzenedithiol, and 1,2-ethanedithiol yielded the dirhenium complexes Re(2)(CO)(6)(mu-eta(4)-SC(6)H(3)(CH(3))S-SC(6)H(3)(CH(3))S) (3), Re(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S) (4), and Re(2)(CO)(6)(SCH(2)CH(2)S-SCH(2)CH(2)S) (5), respectively. In contrast, treatment of Mn(2)(CO)(10) with 1,3-propanedithiol afforded the trimanganese compound Mn(3)(CO)(6)(mu-eta(2)-SCH(2)CH(2)CH(2)S)(3) (6), whereas Re(2)(CO)(10) gave only intractable materials. The molecular structures of 1, 3, and 6 have been determined by single-crystal X-ray diffraction studies. The dimanganese and dirhenium carbonyl compounds 1-5contain a binucleating disulfide ligand, formed by interligand disulfide bond formation between two dithiolate ligands identical in structure to that of the previously reported dimanganese complex Mn(2)(CO)(6)(mu-eta(4)-SC(6)H(4)S-SC(6)H(4)S). Complex 6, on the other hand, forms a unique example of a mixed-valence trimangenese carbonyl compound containing three bridging 1,3-propanedithiolate ligands. The solution properties of 6 have been investigated by UV-vis and EPR spectroscopies as well as electrochemical techniques.

  10. Novel decavanadate cluster complexes [H2V10O28][LH]4·nH2O (L = Imidazole, n = 2 or 2-methylimidazole, n = 0): Preparation, characterization and genotoxic studies

    NASA Astrophysics Data System (ADS)

    Siddiqi, Zafar A.; Anjuli; Sharma, Prashant K.; Shahid, M.; Khalid, Mohd.; Siddique, Armeen; Kumar, Sarvendra

    2012-12-01

    The title complexes were obtained from the reaction of VOSO4 with imidazole or 2-methyl imidazole in presence of adipic acid/iminodiacetic acid. X-ray crystallographic investigations on [H2V10O28](2-MeImzH)4 (2) revealed a strong interaction between decavanadate anion and the protonated ligand moieties as counter cations to stabilize the crystal motif resulting in a high symmetry 2D sheet network. The cyclic voltammetry of (2) suggested formation of a quasi-reversible redox (VV/IV) couple in the solution. The genotoxic studies employing single cell gel electrophoresis (comet assay) confirmed the non-toxic nature of the compounds.

  11. Globular Clusters and Spur Clusters in NGC 4921, the Brightest Spiral Galaxy in the Coma Cluster

    NASA Astrophysics Data System (ADS)

    Lee, Myung Gyoon; Jang, In Sung

    2016-03-01

    We resolve a significant fraction of globular clusters (GCs) in NGC 4921, the brightest spiral galaxy in the Coma cluster. We also find a number of extended bright star clusters (star complexes) in the spur region of the arms. The latter are much brighter and bluer than those in the normal star-forming region, being as massive as 3 × 105 M⊙. The color distribution of the GCs in this galaxy is found to be bimodal. The turnover magnitudes of the luminosity functions of the blue (metal-poor) GCs (0.70 < (V - I) ≤ 1.05) in the halo are estimated V(max) = 27.11 ± 0.09 mag and I(max) = 26.21 ± 0.11 mag. We obtain similar values for NGC 4923, a companion S0 galaxy, and two Coma cD galaxies (NGC 4874 and NGC 4889). The mean value for the turnover magnitudes of these four galaxies is I(max) = 26.25 ± 0.03 mag. Adopting MI (max) = -8.56 ± 0.09 mag for the metal-poor GCs, we determine the mean distance to the four Coma galaxies to be 91 ± 4 Mpc. Combining this with the Coma radial velocity, we derive a value of the Hubble constant, H0 = 77.9 ± 3.6 km s-1 Mpc-1. We estimate the GC specific frequency of NGC 4921 to be SN = 1.29 ± 0.25, close to the values for early-type galaxies. This indicates that NGC 4921 is in the transition phase to S0s.

  12. The binuclear nickel center in the A-cluster of acetyl-CoA synthase (ACS) and two biomimetic dinickel complexes studied by X-ray absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Schrapers, P.; Mebs, S.; Ilina, Y.; Warner, D. S.; Wörmann, C.; Schuth, N.; Kositzki, R.; Dau, H.; Limberg, C.; Dobbek, H.; Haumann, M.

    2016-05-01

    Acetyl-CoA synthase (ACS) is involved in the bacterial carbon oxide conversion pathway. The binuclear nickel sites in ACS enzyme and two biomimetic synthetic compounds containing a Ni(II)Ni(II) unit (1 and 2) were compared using XAS/XES. EXAFS analysis of ACS proteins revealed similar Ni-N/O/S bond lengths and Ni-Ni/Fe distances as in the crystal structure in oxidized ACS, but elongated Ni-ligand bonds in reduced ACS, suggesting more reduced nickel species. The XANES spectra of ACS and the dinickel complexes showed overall similar shapes, but less resolved pre-edge and edge features in ACS, attributed to more distorted square-planar nickel sites in particular in reduced ACS. DFT calculation of pre-edge absorption and Kβ2,5 emission features reproduced the experimental spectra of the synthetic complexes, was sensitive even to the small geometry differences in 1 and 2, and indicated low-spin Ni(II) sites. Comparison of nickel sites in proteins and biomimetic compounds is valuable for deducing structural and electronic differences in response to ligation and redox changes.

  13. Star Cluster Buzzing With Pulsars

    NASA Astrophysics Data System (ADS)

    2005-01-01

    left after a massive star explodes as a supernova at the end of its life. The pulsars in Terzan 5 are the product of a complex history. The stars in the cluster formed about 10 billion years ago, the astronomers say. Some of the most massive stars in the cluster exploded and left the neutron stars as their remnants after only a few million years. Normally, these neutron stars would no longer be seen as swiftly-rotating pulsars: their spin would have slowed because of the "drag" of their intense magnetic fields until the "lighthouse" effect is no longer observable. The Green Bank Telescope The Robert C. Byrd Green Bank Telescope CREDIT: NRAO/AUI/NSF (Click on image for GBT gallery) However, the dense concentration of stars in the cluster gave new life to the pulsars. In the core of a globular cluster, as many as a million stars may be packed into a volume that would fit easily between the Sun and our nearest neighbor star. In such close quarters, stars can pass near enough to form new binary pairs, split apart such pairs, and binary systems even can trade partners, like an elaborate cosmic square dance. When a neutron star pairs up with a "normal" companion star, its strong gravitational pull can draw material off the companion onto the neutron star. This also transfers some of the companion's spin, or angular momentum, to the neutron star, thereby "recycling" the neutron star into a rapidly-rotating millisecond pulsar. In Terzan 5, all the pulsars discovered are rotating rapidly as a result of this process. Astronomers previously had discovered three pulsars in Terzan 5, some 28,000 light-years distant in the constellation Sagittarius, but suspected there were more. On July 17, 2004, Ransom and his colleagues used the GBT, and, in a 6-hour observation, found 14 new pulsars, the most ever found in a single observation. "This was possible because of the great sensitivity of the GBT and the new capabilities of our backend processor," said Ingrid Stairs, a professor at the

  14. Clustering granulometric features

    NASA Astrophysics Data System (ADS)

    Brun, Marcel; Balagurunathan, Yoganand; Barrera, Junior; Dougherty, Edward R.

    2002-05-01

    Granulometric features have been widely used for classification, segmentation and recently in estimation of parameters in shape models. In this paper we study the inference of clustering based on granulometric features for a collection of structuring probes in the context of random models. We use random Boolean models to represent grains of different shapes and structure. It is known that granulometric features are excellent descriptors of shape and structure of grains. Inference based on clustering these features helps to analyze the consistency of these features and clustering algorithms. This greatly aids in classifier design and feature selection. Features and the order of their addition play a role in reducing the inference errors. We study four different types of feature addition methods and the effect of replication in reducing the inference errors.

  15. The spatial structure of young stellar clusters

    NASA Astrophysics Data System (ADS)

    Kuhn, Michael A.

    Star formation is an extremely active area of astronomical research, and young stellar clusters in our Galaxy offer a useful laboratory where star-formation processes can be studied. Young stars form from the the gravitational collapse of molecular clouds that have a hierarchical spatial structure. This leads to stars forming in clustered environments, often with thousands of other young stars in environments that are strongly affected by feedback from massive O-type stars. The environments in these massive star-forming regions (MSFR) can affect how stars form and whether the young stellar clusters remain bound after star formation ends, both of which are questions that have received considerable attention from researchers. Studies of stellar populations in Galactic MSFRs are made difficult due to large numbers of fields stars in the Galactic Plane, large areas of the sky that must be surveyed, high optical extinction from dust, and nebulosity in the the optical and infrared. The Massive Young Star-Forming Complex Study in Infrared and X-ray (MYStIX) uses multiwavelength observations to overcome some of these difficulties, providing some of the most complete, clean membership lists for 20 MSFRs within 3.6 kpc of the Sun. I described X-ray catalogs and mid-infrared catalogs that were used in this survey. The spatial distribution of young stars in 17 MYStIX regions are used to probe the origin and dynamics of the young stellar clusters. Intrinsic stellar surface-density maps are made for each region, which reveal complex structures with dense subclusters. I examine in detail one of the nearest MYStIX young stellar clusters, W 40 (d = 500 pc), which has properties similar to many of the subclusters in more massive and more distant star-forming regions. The cluster in W 40 has a simple structure with mass segregation, indicating that it has undergone dynamical evolution, even though its young age (~0.8 Myr) is insufficient for relaxation from two-body interactions

  16. Hexaruthenium carbonyl cluster complexes with basal edge-bridged square pyramidal metallic skeleton: efficient synthesis of 2-imidopyridine derivatives and determination of their reactive sites in carbonyl substitution reactions.

    PubMed

    Cabeza, Javier A; del Río, Ignacio; García-Alvarez, Pablo; Miguel, Daniel; Riera, Víctor

    2004-08-23

    The reactions of [Ru(3)(CO)(12)] with half equivalent of 2-amino-6-methylpyridine (H(2)ampy) or 2-aminopyridine (H(2)apy) in refluxing xylene give the hexanuclear products [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-L)(mu-CO)(2)(CO)(14)] (L = ampy, 1; apy, 2). These reactions represent the first high-yield syntheses of hexanuclear complexes with a basal edge-bridged square pyramidal metallic skeleton. Five metal atoms of these complexes are bridged by the N-donor ligand in such a way that the edge-bridging metal atom is attached to the pyridine nitrogen, while the basal atoms of the square pyramid are capped by an imido fragment that arises from the activation of both N-H bonds of the NH(2) group. The reactive sites of these complexes in CO substitution reactions have been determined by studying the reactivity of 1 with triphenylphosphine. Two kinetically controlled monosubstitutions take place on the edge-bridging metal atom in positions cis to the pyridine nitrogen, leading to a mixture of two isomers of formula [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(13)(PPh(3))] (3 and 4). On heating at 80 degrees C, these monosubstituted isomers are transformed, via a dissociative pathway, into the product of thermodynamic control (5), which has the PPh(3) ligand on the apical Ru atom. The di- and trisubstituted derivatives [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(PPh(3))(2)] (6) and [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(11)(PPh(3))(3)] (7) are stepwise formed from 3-5 and PPh(3). Compound 6 has the PPh(3) ligands on the edge-bridging and apical Ru atoms, and compound 7 has an additional PPh(3) ligand on an unbridged basal Ru atom. The compound [Ru(6)(mu(3)-H)(2)(mu(5)-eta(2)-ampy)(mu-CO)(2)(CO)(12)(mu-dppm)] (8), in which a basal and the apical Ru atoms are spanned by the dppm ligand, has been isolated from the reaction of 1 with bis(diphenylphosphino)methane.

  17. What determines the stellar mass functions in globular clusters?

    NASA Technical Reports Server (NTRS)

    Djorgovski, S.; Piotto, Giampaolo; Capaccioli, Massimo

    1993-01-01

    We analyze the dependence of stellar mass function slopes for a sample of 17 globular clusters on a variety of cluster parameters. The principal novelty of our approach is the use of appropriate multivariate statistical methods to disentangle the complex situation which is present in this problem: the slopes depend simultaneously on more than one variable, and many cluster parameters are mutually correlated. We find that the mass function slopes in the range M/M(solar) = 0.5-0.8 are largely determined by the position in the Galaxy and to a lesser extent by the cluster metallicity. Clusters closer to the Galactic center or plane have shallower mass function slopes. At a given distance to the Galactic center, clusters closer to the Galactic plane have shallower mass function slopes. At a given R(GC) and/or Z(GP), more metal-rich clusters have shallower mass function slopes. Thus, the monovariate correlations with the position or metallicity are both correct, but only partial, and in terms of slopes, biased descriptions of the situation. We present trivariate least-squares solutions where the mass function slopes can be predicted within the measurement accuracy. This relation can serve as a powerful observational constraint for theories of globular cluster formation and evolution, and it is one of the tightest correlations between globular cluster properties now known.

  18. The Impact of Large Scale Environments on Cluster Entropy Profiles

    NASA Astrophysics Data System (ADS)

    Trierweiler, Isabella; Su, Yuanyuan

    2017-01-01

    We perform a systematic analysis of 21 clusters imaged by the Suzaku satellite to determine the relation between the richness of cluster environments and entropy at large radii. Entropy profiles for clusters are expected to follow a power-law, but Suzaku observations show that the entropy profiles of many clusters are significantly flattened beyond 0.3 Rvir. While the entropy at the outskirts of clusters is thought to be highly dependent on the large scale cluster environment, the exact nature of the environment/entropy relation is unclear. Using the Sloan Digital Sky Survey and 6dF Galaxy Survey, we study the 20 Mpc large scale environment for all clusters in our sample. We find no strong relation between the entropy deviations at the virial radius and the total luminosity of the cluster surroundings, indicating that accretion and mergers have a more complex and indirect influence on the properties of the gas at large radii. We see a possible anti-correlation between virial temperature and richness of the cluster environment and find that density excess appears to play a larger role in the entropy flattening than temperature, suggesting that clumps of gas can lower entropy.

  19. Young Clusters in Nearby, Grand-Design Spirals

    NASA Astrophysics Data System (ADS)

    Grosbøl, Preben; Dottori, Horacio

    The distributions of stellar clusters in 10 nearby, grand-design spiral galaxies were studied using deep JHK-maps from HAWK-I/VLT. The properties of the cluster complexes were analyzed using (H-K)-(J-H) diagrams. Two groups of clusters can be identified where the main one is associated to old clusters with low extinction while the other, less populated, consists of very young clusters (i.e. < 10 Myr) with an average reddening around A_{V} ˜ 7m. The (J-K)-MK diagrams show two branches of clusters populated by old and young clusters, respectively. The gap between them suggests a rapid reduction of extinction in the clusters at an early evolutionary phase. Statistical tests, taking the sample sizes into account, show that the cluster distribution functions (CDF) are different in arm and inter-arm regions, for strong spiral perturbations, with the former being shifted to brighter magnitudes by at least 0.4m. Also the star formation rates in the strong arms were found to be 2-5 times higher than those in the inter-arm regions.

  20. Ordered Subspace Clustering With Block-Diagonal Priors.

    PubMed

    Wu, Fei; Hu, Yongli; Gao, Junbin; Sun, Yanfeng; Yin, Baocai

    2016-12-01

    Many application scenarios involve sequential data, but most existing clustering methods do not well utilize the order information embedded in sequential data. In this paper, we study the subspace clustering problem for sequential data and propose a new clustering method, namely ordered sparse clustering with block-diagonal prior (BD-OSC). Instead of using the sparse normalizer in existing sparse subspace clustering methods, a quadratic normalizer for the data sparse representation is adopted to model the correlation among the data sparse coefficients. Additionally, a block-diagonal prior for the spectral clustering affinity matrix is integrated with the model to improve clustering accuracy. To solve the proposed BD-OSC model, which is a complex optimization problem with quadratic normalizer and block-diagonal prior constraint, an efficient algorithm is proposed. We test the proposed clustering method on several types of databases, such as synthetic subspace data set, human face database, video scene clips, motion tracks, and dynamic 3-D face expression sequences. The experiments show that the proposed method outperforms state-of-the-art subspace clustering methods.

  1. Infrared Multiple Photon Dissociation Spectroscopy Of Metal Cluster-Adducts

    NASA Astrophysics Data System (ADS)

    Cox, D. M.; Kaldor, A.; Zakin, M. R.

    1987-01-01

    Recent development of the laser vaporization technique combined with mass-selective detection has made possible new studies of the fundamental chemical and physical properties of unsupported transition metal clusters as a function of the number of constituent atoms. A variety of experimental techniques have been developed in our laboratory to measure ionization threshold energies, magnetic moments, and gas phase reactivity of clusters. However, studies have so far been unable to determine the cluster structure or the chemical state of chemisorbed species on gas phase clusters. The application of infrared multiple photon dissociation IRMPD to obtain the IR absorption properties of metal cluster-adsorbate species in a molecular beam is described here. Specifically using a high power, pulsed CO2 laser as the infrared source, the IRMPD spectrum for methanol chemisorbed on small iron clusters is measured as a function of the number of both iron atoms and methanols in the complex for different methanol isotopes. Both the feasibility and potential utility of IRMPD for characterizing metal cluster-adsorbate interactions are demonstrated. The method is generally applicable to any cluster or cluster-adsorbate system dependent only upon the availability of appropriate high power infrared sources.

  2. 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

  3. Health Occupations Cluster.

    ERIC Educational Resources Information Center

    Walraven, Catherine; And Others

    These instructional materials consist of a series of curriculum worksheets that cover tasks to be mastered by students in health occupations cluster programs. Covered in the curriculum worksheets are diagnostic procedures; observing/recording/reporting/planning; safety; nutrition/elimination; hygiene/personal care/comfort;…

  4. Clustering in Bubble Suspensions

    NASA Astrophysics Data System (ADS)

    Zenit, Roberto

    2000-11-01

    A monidisperse bubble suspension is studied experimentally for the limit in which the Weber number is small and the Reynolds number is large. For this regime the suspension can be modeled using potential flow theory to describe the dynamics of the interstitial fluid. Complete theoretical descriptions have been composed (Spelt and Sangani, 1998) to model the behavior of these suspensions. Bubble clustering is a natural instability that arises from the potential flow considerations, in which bubbles tend to align in horizontal rafts as they move upwards. The appearance of bubble clusters was recently corroborated experimentally by Zenit et al. (2000), who found that although clusters did appear, their strength was not as strong as the predictions. Experiments involving gravity driven shear flows are used to explain the nature of the clustering observed in these type of flows. Balances of the bubble phase pressure (in terms of a calculated diffusion coefficient) and the Maxwell pressure (from the potential flow description) are presented to predict the stability of the bubble suspension. The predictions are compared with experimental results.

  5. FUEL ROD CLUSTERS

    DOEpatents

    Schultz, A.B.

    1959-08-01

    A cluster of nuclear fuel rods and a tubular casing therefor through which a coolant flows in heat-exchange contact with the fuel rods is described. The fuel rcds are held in the casing by virtue of the compressive force exerted between longitudinal ribs of the fuel rcds and internal ribs of the casing or the internal surfaces thereof.

  6. Hydrodynamics of Merging Clusters

    NASA Technical Reports Server (NTRS)

    David,Laurence; Mushotzky, Richard F. (Technical Monitor)

    2004-01-01

    With the Chandra X-Ray Observatory, we observed two clusters of galaxies that are undergoing major mergers . All of the analysis is complete and two papers have been accepted for publication. The abstracts of the two papers are presented in the report.

  7. PVM Support for Clusters

    NASA Technical Reports Server (NTRS)

    Springer, P.

    2000-01-01

    The latest version of PVM (3.4.3) now contains support for a PC cluster running Linux, also known as a Beowulf system. A PVM user of a computer outside the Beowulf system can add the Beowulf as a single machine.

  8. Nuclear Cluster Physics

    SciTech Connect

    Kamimura, Masayasu

    2011-05-06

    Predictive power of theory needs good models and accurate calculation methods to solve the Schroedinger equations of the systems concerned. We present some examples of successful predictions based on the nuclear cluster models of light nuclei and hypernuclei and on the calculation methods that have been developed by Kyushu group.

  9. Cluster headaches simulating parasomnias.

    PubMed

    Isik, Ugur; D'Cruz, O 'Neill F

    2002-09-01

    Nocturnal episodes of agitated arousal in otherwise healthy young children are often related to nonrapid eye movement parasomnias (night terrors). However, in patients with acute onset or increased frequency of parasomnias, organic causes of discomfort must be excluded. We report four young children whose parasomnias were caused by nocturnal cluster headaches and who responded to indomethacin dramatically.

  10. Clustered for Success

    ERIC Educational Resources Information Center

    Brulles, Dina; Winebrenner, Susan

    2012-01-01

    Schools need to address the needs of their students with high ability. Not only does this raise achievement levels schoolwide, it also attracts students from surrounding districts and recaptures advanced learners who left the school because their needs weren't being met. One practical intervention--cluster grouping--provides an inclusive…

  11. Health Occupations Cluster Guide.

    ERIC Educational Resources Information Center

    Oregon State Dept. of Education, Salem.

    Intended to assist the vocational teacher in designing and implementing a cluster program in health occupations, this guide suggests ideas for teaching the specific knowledge and skills that qualify students for entry-level employment in the health occupations field. The knowledge and skills are applicable to 12 occupations: dental assistant;…

  12. Buckets, Clusters and Dienst

    NASA Technical Reports Server (NTRS)

    Nelson, Michael L.; Maly, Kurt; Shen, Stewart N. T.

    1997-01-01

    In this paper we describe NCSTRL+, a unified, canonical digital library for scientific and technical information (STI). NCSTRL+ is based on the Networked Computer Science Technical Report Library (NCSTRL), a World Wide Web (WWW) accessible digital library (DL) that provides access to over 80 university departments and laboratories. NCSTRL+ implements two new technologies: cluster functionality and publishing "buckets." We have extended the Dienst protocol, the protocol underlying NCSTRL, to provide the ability to "cluster" independent collections into a logically centralized digital library based upon subject category classification, type of organization, and genres of material. The concept of "buckets" provides a mechanism for publishing and managing logically linked entities with multiple data formats. The NCSTRL+ prototype DL contains the holdings of NCSTRL and the NASA Technical Report Server (NTRS). The prototype demonstrates the feasibility of publishing into a multi-cluster DL, searching across clusters, and storing and presenting buckets of information. We show that the overhead for these additional capabilities is minimal to both the author and the user when compared to the equivalent process within NCSTRL.

  13. Universality of cluster dynamics

    NASA Astrophysics Data System (ADS)

    McFadden, Carson; Bouchard, Louis-S.

    2010-12-01

    We have studied the kinetics of cluster formation for dynamical systems of dimensions up to n=8 interacting through elastic collisions or coalescence. These systems could serve as possible models for gas kinetics, polymerization, and self-assembly. In the case of elastic collisions, we found that the cluster size probability distribution undergoes a phase transition at a critical time which can be predicted from the average time between collisions. This enables forecasting of rare events based on limited statistical sampling of the collision dynamics over short time windows. The analysis was extended to Lp -normed spaces (p=1,…,∞) to allow for some amount of interpenetration or volume exclusion. The results for the elastic collisions are consistent with previously published low-dimensional results in that a power law is observed for the empirical cluster size distribution at the critical time. We found that the same power law also exists for all dimensions n=2,…,8 , two-dimensional Lp norms, and even for coalescing collisions in two dimensions. This broad universality in behavior may be indicative of a more fundamental process governing the growth of clusters.

  14. Curriculum Guide Construction Cluster.

    ERIC Educational Resources Information Center

    Kline, Ken

    As part of a model construction cluster curriculum development project, this guide was developed and implemented in the Beaverton (Oregon) School District. The curriculum guide contains 16 units covering the following topics: introduction to construction jobs; safety and first aid; blueprint readings; basic mathematics; site work; framing; roofing…

  15. Hybrid cluster identification

    NASA Astrophysics Data System (ADS)

    Martín-Herrero, J.

    2004-10-01

    I present a hybrid method for the labelling of clusters in two-dimensional lattices, which combines the recursive approach with iterative scanning to reduce the stack size required by the pure recursive technique, while keeping its benefits: single pass and straightforward cluster characterization and percolation detection parallel to the labelling. While the capacity to hold the entire lattice in memory is usually regarded as the major constraint for the applicability of the recursive technique, the required stack size is the real limiting factor. Resorting to recursion only for the transverse direction greatly reduces the recursion depth and therefore the required stack. It also enhances the overall performance of the recursive technique, as is shown by results on a set of uniform random binary lattices and on a set of samples of the Ising model. I also show how this technique may replace the recursive technique in Wolff's cluster algorithm, decreasing the risk of stack overflow and increasing its speed, and the Hoshen-Kopelman algorithm in the Swendsen-Wang cluster algorithm, allowing effortless characterization during generation of the samples and increasing its speed.

  16. Linked supramolecular building blocks for enhanced cluster formation

    DOE PAGES

    McLellan, Ross; Palacios, Maria A.; Beavers, Christine M.; ...

    2015-01-09

    Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis-calix[4]arenes and transition metal ions or 3d-4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.

  17. Linked supramolecular building blocks for enhanced cluster formation

    SciTech Connect

    McLellan, Ross; Palacios, Maria A.; Beavers, Christine M.; Teat, Simon J.; Piligkos, Stergios; Brechin, Euan K.; Dalgarno, Scott J.

    2015-01-09

    Methylene-bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis-calix[4]arenes and transition metal ions or 3d-4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures.

  18. Countdown for the Cluster quartet

    NASA Astrophysics Data System (ADS)

    2000-07-01

    the first pair of Clusters on 15 July will be covered live also on the Internet by ESA at http://clusterlaunch.esa.int and also by Spaceflight Now at http://spaceflightnow.com Note for editors. ESA's Cluster II mission will study the complex interaction between the Sun and Earth in unprecedented detail. For the first time, four satellites will fly in close formation above the Earth's poles, studying the magnetic field around our planet and its continual battle with the energetic particles of the solar wind. This groundbreaking mission to explore the magnetosphere and provide the first small-scale, three-dimensional 'map' of near-Earth space is one of the key Cornerstones in ESA's Horizons 2000 long term science programme. For more information on the winning entries, visit the ESA Science Website at: http://sci.esa.int/cluster/competition For interviews with the winners up to 10 July, 2000, please contact: Martine Caparros, tel:+31 71 565 3183, fax: +31 71 565 4101, E-mail: mcaparro@estec.esa.nl Further information on the Cluster II mission - including regular updates from Baikonur - can be found on the Internet at: http://sci.esa.int/cluster/ ESA Communication Department, Media Relations Office Tel: +33(0)1. 53.69.7155 Fax: +33(0)1.53.69 7690 Further information on ESA at http://www.esa.int

  19. Phase behavior of the 38-atom Lennard-Jones cluster.

    PubMed

    Sehgal, Ray M; Maroudas, Dimitrios; Ford, David M

    2014-03-14

    We have developed a coarse-grained description of the phase behavior of the isolated 38-atom Lennard-Jones cluster (LJ38). The model captures both the solid-solid polymorphic transitions at low temperatures and the complex cluster breakup and melting transitions at higher temperatures. For this coarse model development, we employ the manifold learning technique of diffusion mapping. The outcome of the diffusion mapping analysis over a broad temperature range indicates that two order parameters are sufficient to describe the cluster's phase behavior; we have chosen two such appropriate order parameters that are metrics of condensation and overall crystallinity. In this well-justified coarse-variable space, we calculate the cluster's free energy landscape (FEL) as a function of temperature, employing Monte Carlo umbrella sampling. These FELs are used to quantify the phase behavior and onsets of phase transitions of the LJ38 cluster.

  20. Phase behavior of the 38-atom Lennard-Jones cluster

    SciTech Connect

    Sehgal, Ray M.; Maroudas, Dimitrios E-mail: ford@ecs.umass.edu; Ford, David M. E-mail: ford@ecs.umass.edu

    2014-03-14

    We have developed a coarse-grained description of the phase behavior of the isolated 38-atom Lennard-Jones cluster (LJ{sub 38}). The model captures both the solid-solid polymorphic transitions at low temperatures and the complex cluster breakup and melting transitions at higher temperatures. For this coarse model development, we employ the manifold learning technique of diffusion mapping. The outcome of the diffusion mapping analysis over a broad temperature range indicates that two order parameters are sufficient to describe the cluster's phase behavior; we have chosen two such appropriate order parameters that are metrics of condensation and overall crystallinity. In this well-justified coarse-variable space, we calculate the cluster's free energy landscape (FEL) as a function of temperature, employing Monte Carlo umbrella sampling. These FELs are used to quantify the phase behavior and onsets of phase transitions of the LJ{sub 38} cluster.

  1. Dynamics of small mobile helium clusters near tungsten surfaces

    NASA Astrophysics Data System (ADS)

    Hu, Lin; Hammond, Karl D.; Wirth, Brian D.; Maroudas, Dimitrios

    2014-08-01

    We report the results of a systematic atomic-scale analysis of the dynamics of small mobile helium clusters in tungsten, near tungsten surfaces. These helium clusters are attracted to tungsten surfaces due to an elastic interaction force that drives surface segregation. As the clusters migrate toward the surface, trap mutation and cluster dissociation are activated at rates higher than in the bulk. These kinetic processes are responsible for important structural, morphological, and compositional features in plasma-exposed tungsten, including surface adatoms, near-surface immobile helium-vacancy complexes, and retained helium content. Detailed results are presented for di-helium and tri-helium clusters near low-Miller-index tungsten surfaces.

  2. Clustering algorithms for Stokes space modulation format recognition.

    PubMed

    Boada, Ricard; Borkowski, Robert; Monroy, Idelfonso Tafur

    2015-06-15

    Stokes space modulation format recognition (Stokes MFR) is a blind method enabling digital coherent receivers to infer modulation format information directly from a received polarization-division-multiplexed signal. A crucial part of the Stokes MFR is a clustering algorithm, which largely influences the performance of the detection process, particularly at low signal-to-noise ratios. This paper reports on an extensive study of six different clustering algorithms: k-means, expectation maximization, density-based DBSCAN and OPTICS, spectral clustering and maximum likelihood clustering, used for discriminating between dual polarization: BPSK, QPSK, 8-PSK, 8-QAM, and 16-QAM. We determine essential performance metrics for each clustering algorithm and modulation format under test: minimum required signal-to-noise ratio, detection accuracy and algorithm complexity.

  3. STAR FORMATION ACROSS THE W3 COMPLEX

    SciTech Connect

    Román-Zúñiga, Carlos G.; Ybarra, Jason E.; Tapia, Mauricio; Megías, Guillermo D.; Lada, Elizabeth A.; Alves, Joáo F.

    2015-09-15

    We present a multi-wavelength analysis of the history of star formation in the W3 complex. Using deep, near-infrared ground-based images combined with images obtained with Spitzer and Chandra observatories, we identified and classified young embedded sources. We identified the principal clusters in the complex and determined their structure and extension. We constructed extinction-limited samples for five principal clusters and constructed K-band luminosity functions that we compare with those of artificial clusters with varying ages. This analysis provided mean ages and possible age spreads for the clusters. We found that IC 1795, the centermost cluster of the complex, still hosts a large fraction of young sources with circumstellar disks. This indicates that star formation was active in IC 1795 as recently as 2 Myr ago, simultaneous to the star-forming activity in the flanking embedded clusters, W3-Main and W3(OH). A comparison with carbon monoxide emission maps indicates strong velocity gradients in the gas clumps hosting W3-Main and W3(OH) and shows small receding clumps of gas at IC 1795, suggestive of rapid gas removal (faster than the T Tauri timescale) in the cluster-forming regions. We discuss one possible scenario for the progression of cluster formation in the W3 complex. We propose that early processes of gas collapse in the main structure of the complex could have defined the progression of cluster formation across the complex with relatively small age differences from one group to another. However, triggering effects could act as catalysts for enhanced efficiency of formation at a local level, in agreement with previous studies.

  4. Star Formation Across the W3 Complex

    NASA Astrophysics Data System (ADS)

    Román-Zúñiga, Carlos G.; Ybarra, Jason E.; Megías, Guillermo D.; Tapia, Mauricio; Lada, Elizabeth A.; Alves, Joáo F.

    2015-09-01

    We present a multi-wavelength analysis of the history of star formation in the W3 complex. Using deep, near-infrared ground-based images combined with images obtained with Spitzer and Chandra observatories, we identified and classified young embedded sources. We identified the principal clusters in the complex and determined their structure and extension. We constructed extinction-limited samples for five principal clusters and constructed K-band luminosity functions that we compare with those of artificial clusters with varying ages. This analysis provided mean ages and possible age spreads for the clusters. We found that IC 1795, the centermost cluster of the complex, still hosts a large fraction of young sources with circumstellar disks. This indicates that star formation was active in IC 1795 as recently as 2 Myr ago, simultaneous to the star-forming activity in the flanking embedded clusters, W3-Main and W3(OH). A comparison with carbon monoxide emission maps indicates strong velocity gradients in the gas clumps hosting W3-Main and W3(OH) and shows small receding clumps of gas at IC 1795, suggestive of rapid gas removal (faster than the T Tauri timescale) in the cluster-forming regions. We discuss one possible scenario for the progression of cluster formation in the W3 complex. We propose that early processes of gas collapse in the main structure of the complex could have defined the progression of cluster formation across the complex with relatively small age differences from one group to another. However, triggering effects could act as catalysts for enhanced efficiency of formation at a local level, in agreement with previous studies.

  5. PDMS embedded Ag clusters: Coalescence and cluster-matrix interaction

    NASA Astrophysics Data System (ADS)

    Roese, S.; Engemann, D.; Hoffmann, S.; Latussek, K.; Sternemann, C.; Hövel, H.

    2016-05-01

    Polydimethylsiloxane (PDMS) has proven to be a suitable embedding medium for silver clusters to prevent aggregation. In order to investigate the influence of the PDMS on the electronic and local atomic structure of the clusters the measurement of x-ray absorption near edge structure (XANES) spectra for different coverages of silver clusters in PDMS and calculations of corresponding XANES spectra have been performed. The coalescence process and the cluster-PDMS interaction were investigated with XANES.

  6. Identification of the cluster control region for the protocadherin-beta genes located beyond the protocadherin-gamma cluster.

    PubMed

    Yokota, Shinnichi; Hirayama, Teruyoshi; Hirano, Keizo; Kaneko, Ryosuke; Toyoda, Shunsuke; Kawamura, Yoshimi; Hirabayashi, Masumi; Hirabayashi, Takahiro; Yagi, Takeshi

    2011-09-09

    The clustered protocadherins (Pcdhs), Pcdh-α, -β, and -γ, are transmembrane proteins constituting a subgroup of the cadherin superfamily. Each Pcdh cluster is arranged in tandem on the same chromosome. Each of the three Pcdh clusters shows stochastic and combinatorial expression in individual neurons, thus generating a hugely diverse set of possible cell surface molecules. Therefore, the clustered Pcdhs are candidates for determining neuronal molecular diversity. Here, we showed that the targeted deletion of DNase I hypersensitive (HS) site HS5-1, previously identified as a Pcdh-α regulatory element in vitro, affects especially the expression of specific Pcdh-α isoforms in vivo. We also identified a Pcdh-β cluster control region (CCR) containing six HS sites (HS16, 17, 17', 18, 19, and 20) downstream of the Pcdh-γ cluster. This CCR comprehensively activates the expression of the Pcdh-β gene cluster in cis, and its deletion dramatically decreases their expression levels. Deleting the CCR nonuniformly down-regulates some Pcdh-γ isoforms and does not affect Pcdh-α expression. Thus, the CCR effect extends beyond the 320-kb region containing the Pcdh-γ cluster to activate the upstream Pcdh-β genes. Thus, we concluded that the CCR is a highly specific regulatory unit for Pcdh-β expression on the clustered Pcdh genomic locus. These findings suggest that each Pcdh cluster is controlled by distinct regulatory elements that activate their expression and that the stochastic gene regulation of the clustered Pcdhs is controlled by the complex chromatin architecture of the clustered Pcdh locus.

  7. INTER- AND INTRA-CLUSTER AGE GRADIENTS IN MASSIVE STAR FORMING REGIONS AND INDIVIDUAL NEARBY STELLAR CLUSTERS REVEALED BY MYStIX

    NASA Astrophysics Data System (ADS)

    Getman, Konstantin V.; Feigelson, Eric; Kuhn, Michael A.; Broos, Patrick S; Townsley, Leisa K.; Naylor, Tim; Povich, Matthew S.; Luhman, Kevin; Garmire, Gordon

    2014-08-01

    The MYStIX (Massive Young Star-Forming Complex Study in Infrared and X-ray) project seeks to characterize 20 OB-dominated young star forming regions (SFRs) at distances <4 kpc using photometric catalogs from the Chandra X-ray Observatory, Spitzer Space Telescope, UKIRT and 2MASS surveys. As part of the MYStIX project, we developed a new stellar chronometer that employs near-infrared and X-ray photometry data, AgeJX. Computing AgeJX averaged over MYStIX (sub)clusters reveals previously unknown age gradients across most of the MYStIX regions as well as within some individual rich clusters. Within the SFRs, the inferred AgeJX ages are youngest in obscured locations in molecular clouds, intermediate in revealed stellar clusters, and oldest in distributed stellar populations. Noticeable intra-cluster gradients are seen in the NGC 2024 (Flame Nebula) star cluster and the Orion Nebula Cluster (ONC): stars in cluster cores appear younger and thus were formed later than stars in cluster halos. The latter result has two important implications for the formation of young stellar clusters. Clusters likely form slowly: they do not arise from a single nearly-instantaneous burst of star formation. The simple models where clusters form inside-out are likely incorrect, and more complex models are needed. We provide several star formation scenarios that alone or in combination may lead to the observed core-halo age gradients.

  8. The Rotation of Galaxy Clusters

    NASA Astrophysics Data System (ADS)

    Tovmassian, H. M.

    2015-09-01

    The method for detection of the galaxy cluster rotation based on the study of distribution of member galaxies with velocities lower and higher than the cluster mean velocity over the cluster image is proposed. The search for rotation is made for flat clusters with a/b > 1.8 and BMI type clusters which are expected to be rotating. For comparison there were studied also round clusters and clusters of NBMI type, the second by brightness galaxy, which does not differ significantly from the cluster cD galaxy. Seventeen out of studied 65 clusters are found to be rotating. It was found that the detection rate is sufficiently high for flat clusters, over 60%, and clusters of BMI type with dominant cD galaxy, ≈ 35% . The obtained results show that clusters were formed from the huge primordial gas clouds and preserved the rotation of the primordial clouds, unless they did not experience mergings with other clusters and groups of galaxies, as a result of which the rotation was prevented.

  9. Femtosecond dynamics of cluster expansion

    NASA Astrophysics Data System (ADS)

    Gao, Xiaohui; Wang, Xiaoming; Shim, Bonggu; Arefiev, Alexey; Tushentsov, Mikhail; Breizman, Boris; Downer, Mike

    2010-03-01

    Noble gas clusters irradiated by intense ultrafast laser expand quickly and become typical plasma in picosecond time scale. During the expansion, the clustered plasma demonstrates unique optical properties such as strong absorption and positive contribution to the refractive index. Here we studied cluster expansion dynamics by fs-time-resolved refractive index and absorption measurements in cluster gas jets after ionization and heating by an intense pump pulse. The refractive index measured by frequency domain interferometry (FDI) shows the transient positive peak of refractive index due to clustered plasma. By separating it from the negative contribution of the monomer plasma, we are able to determine the cluster fraction. The absorption measured by a delayed probe shows the contribution from clusters of various sizes. The plasma resonances in the cluster explain the enhancement of the absorption in our isothermal expanding cluster model. The cluster size distribution can be determined. A complete understanding of the femtosecond dynamics of cluster expansion is essential in the accurate interpretation and control of laser-cluster experiments such as phase-matched harmonic generation in cluster medium.

  10. 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

  11. SAR image change detection using watershed and spectral clustering

    NASA Astrophysics Data System (ADS)

    Niu, Ruican; Jiao, L. C.; Wang, Guiting; Feng, Jie

    2011-12-01

    A new method of change detection in SAR images based on spectral clustering is presented in this paper. Spectral clustering is employed to extract change information from a pair images acquired on the same geographical area at different time. Watershed transform is applied to initially segment the big image into non-overlapped local regions, leading to reduce the complexity. Experiments results and system analysis confirm the effectiveness of the proposed algorithm.

  12. United we stand: big roles for small RNA gene clusters.

    PubMed

    Felden, Brice; Paillard, Luc

    2017-02-01

    Prokaryotes and eukaryotes evolved relatively similar RNA-based molecular mechanisms to fight potentially deleterious nucleic acids coming from phages, transposons, or viruses. Short RNAs guide effector complexes toward their targets to be silenced or eliminated. These short immunity RNAs are transcribed from clustered loci. Unexpectedly and strikingly, bacterial and eukaryotic immunity RNA clusters share substantial functional and mechanistic resemblances in fighting nucleic acid intruders.

  13. 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…

  14. Theoretical illumination of water-inserted structures of the CaMn4O5 cluster in the S2 and S3 states of oxygen-evolving complex of photosystem II: full geometry optimizations by B3LYP hybrid density functional.

    PubMed

    Isobe, H; Shoji, M; Yamanaka, S; Umena, Y; Kawakami, K; Kamiya, N; Shen, J-R; Yamaguchi, K

    2012-11-28

    Full geometry optimizations of several inorganic model clusters, CaMn(4)O(4)XYZ(H(2)O)(2) (X, Y, Z = H(2)O, OH(-) or O(2-)), by the use of the B3LYP hybrid density functional theory (DFT) have been performed to illuminate plausible molecular structures of the catalytic site for water oxidation in the S(0), S(1), S(2) and S(3) states of the Kok cycle for the oxygen-evolving complex (OEC) of photosystem II (PSII). Optimized geometries obtained by the energy gradient method have revealed the degree of symmetry breaking of the unstable three-center Mn(a)-X-Mn(d) bond in CaMn(4)O(4)XYZ(H(2)O)(2). The right-elongated (R) Mn(a)-X···Mn(d) and left-elongated (L) Mn(a)···X-Mn(d) structures appear to occupy local minima on a double-well potential for several key intermediates in these states. The effects of insertion of one extra water molecule to the vacant coordination site, Mn(d) (Mn(a)), for R (L) structures have also been examined in detail. The greater stability of the L-type structure over the R-type has been concluded for key intermediates in the S(2) and S(3) states. Implications of the present DFT structures are discussed in relation to previous DFT and related results, together with recent X-ray diffraction results for model compounds of cubane-like OEC cluster of PSII.

  15. Completing the Chandra survey of the Carina Nebula: the cluster NGC 3293

    NASA Astrophysics Data System (ADS)

    Preibisch, Thomas

    2014-09-01

    We propose to complete and conclude Chandra's investigation of the young star clusters in the Carina Nebula Complex with an observation of the last still un-observed massive cluster, NGC3293. Although NGC3293 is probably the second most massive cluster in the entire complex, its low-mass population is basically unknown. A single ACIS-I pointing will reveal the low-mass cluster members and provide a census of the cluster population and its total mass. This information is urgently needed for the study of the global properties and the history of the Carina Nebula Complex. The Chandra data will also allow us to search for isolated neutron stars that are the remnants of the about 20 supernovae that are thought to have occurred in this cluster and for diffuse X-ray emission.

  16. Ultra-small rhenium clusters supported on graphene.

    PubMed

    Miramontes, Orlando; Bonafé, Franco; Santiago, Ulises; Larios-Rodriguez, Eduardo; Velázquez-Salazar, Jesús J; Mariscal, Marcelo M; Yacaman, Miguel José

    2015-03-28

    The adsorption of very small rhenium clusters (2-13 atoms) supported on graphene was studied by high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM). The atomic structure of the clusters was fully resolved with the aid of density functional theory calculations and STEM simulations. It was found that octahedral and tetrahedral structures work as seeds to obtain more complex morphologies. Finally, a detailed analysis of the electronic structure suggested that a higher catalytic effect can be expected in Re clusters when adsorbed on graphene than in isolated ones.

  17. Ultra-small rhenium clusters supported on graphene

    PubMed Central

    Miramontes, Orlando; Bonafé, Franco; Santiago, Ulises; Larios-Rodriguez, Eduardo; Velázquez-Salazar, Jesús J.; Mariscal, Marcelo M.; Yacaman, Miguel José

    2015-01-01

    The adsorption of very small rhenium clusters (2 – 13 atoms) supported on graphene was studied with high annular dark field - scanning transmission electron microscopy (HAADF-STEM). The atomic structure of the clusters was fully resolved with the aid of density functional calculations and STEM simulations. It was found that octahedral and tetrahedral structures work as seeds to obtain more complex morphologies. Finally, a detailed analysis of the electronic structure suggested that a higher catalytic effect can be expected in Re clusters when adsorbed on graphene than in isolated ones. PMID:25721176

  18. Emergence of Assortative Mixing between Clusters of Cultured Neurons

    PubMed Central

    Teller, Sara; Granell, Clara; De Domenico, Manlio; Soriano, Jordi; Gómez, Sergio; Arenas, Alex

    2014-01-01

    The analysis of the activity of neuronal cultures is considered to be a good proxy of the functional connectivity of in vivo neuronal tissues. Thus, the functional complex network inferred from activity patterns is a promising way to unravel the interplay between structure and functionality of neuronal systems. Here, we monitor the spontaneous self-sustained dynamics in neuronal cultures formed by interconnected aggregates of neurons (clusters). Dynamics is characterized by the fast activation of groups of clusters in sequences termed bursts. The analysis of the time delays between clusters' activations within the bursts allows the reconstruction of the directed functional connectivity of the network. We propose a method to statistically infer this connectivity and analyze the resulting properties of the associated complex networks. Surprisingly enough, in contrast to what has been reported for many biological networks, the clustered neuronal cultures present assortative mixing connectivity values, meaning that there is a preference for clusters to link to other clusters that share similar functional connectivity, as well as a rich-club core, which shapes a ‘connectivity backbone’ in the network. These results point out that the grouping of neurons and the assortative connectivity between clusters are intrinsic survival mechanisms of the culture. PMID:25188377

  19. Animation of the Phoenix Cluster

    NASA Video Gallery

    This animation shows how large numbers of stars form in the Phoenix Cluster. It begins by showing several galaxies in the cluster and hot gas (in red). This hot gas contains more normal matter than...

  20. Nuclear Cluster Aspects in Astrophysics

    NASA Astrophysics Data System (ADS)

    Kubono, Shigeru

    2010-03-01

    The role of nuclear clustering is discussed for nucleosynthesis in stellar evolution with Cluster Nucleosynthesis Diagram (CND) proposed before. Special emphasis is placed on α-induced stellar reactions together with molecular states for O and C burning.

  1. Observations of Distant Clusters

    NASA Technical Reports Server (NTRS)

    Donahue, Megan

    2004-01-01

    The is the proceedings and papers supported by the LTSA grant: Homer, D. J.\\& Donahue, M. 2003, in "The Emergence of Cosmic Structure": 13'h Astrophysics Conference Proceedings, Vol. 666,3 1 1-3 14, (AIP). Baumgartner, W. H., Loewenstein, M., Horner, D. J., Mushotzky, R. F. 2003, HEAD- AAS, 35.3503. Homer, D. J. , Donahue, M., Voit G. M. 2003, HEAD-AAS, 35.1309. Nowak, M. A., Smith, B., Donahue, M., Stocke, J. 2003, HEAD-AAS, 35.1316. Scott, D., Borys, C., Chapman, S. C., Donahue, M., Fahlman, G. G., Halpem, M. Newbury, P. 2002, AAS, 128.01. Jones, L. R. et al. 2002, A new era in cosmology, ASP Conference Proceedings, Vol. 283, p. 223 Donahue, M., Daly, R. A., Homer, D. J. 2003, ApJ, 584, 643, Constraints on the Cluster Environments and Hotspot magnetic field strengths for radio sources 3280 and 3254. Donahue, M., et al. 2003, ApJ, 598, 190. The mass, baryonic fraction, and x-ray temperature of the luminous, high-redshift cluster of galaxies MS045 1.6-0305 Perlman, E. S. et al. 2002, ApJS, 140, 256. Smith, B. J., Nowak, M., Donahue, M., Stocke, J. 2003, AJ, 126, 1763. Chandra Observations of the Interacting NGC44 10 Group of Galaxies. Postman, M., Lauer, T. R., Oegerle, W., Donahue, M. 2002, ApJ, 579, 93. The KPNO/deep-range cluster survey I. The catalog and space density of intermediate-redshift clusters. Molnar, S. M., Hughes, J. P., Donahue, M., Joy, M. 2002, ApJ, 573, L91, Chandra Observations of Unresolved X-Ray Sources around Two Clusters of Galaxies. Donahue, M., Mack, J., 2002 NewAR, 46, 155, HST NIcmos and WFPC2 observations of molecular hydrogen and dust around cooling flows. Koekemoer, A. M. et al. 2002 NewAR, 46, 149, Interactions between the A2597 central radio source and dense gas host galaxy. Donahue, M. et al. 2002 ApJ, 569,689, Distant cluster hunting II.

  2. The next generation Virgo cluster survey. VIII. The spatial distribution of globular clusters in the Virgo cluster

    SciTech Connect

    Durrell, Patrick R.; Accetta, Katharine; Côté, Patrick; Blakeslee, John P.; Ferrarese, Laura; McConnachie, Alan; Gwyn, Stephen; Peng, Eric W.; Zhang, Hongxin; Mihos, J. Christopher; Puzia, Thomas H.; Jordán, Andrés; Lançon, Ariane; Liu, Chengze; Cuillandre, Jean-Charles; Boissier, Samuel; Boselli, Alessandro; Courteau, Stéphane; Duc, Pierre-Alain; and others

    2014-10-20

    slightly lower than but consistent with those derived for individual galactic halos. Taken as a whole, our results show that the production of the complex structures in the unrelaxed Virgo cluster core (including the production of the diffuse intracluster light) is an ongoing and continuing process.

  3. Neurobiology and sleep disorders in cluster headache.

    PubMed

    Barloese, Mads Christian Johannes

    2015-01-01

    Cluster headache is characterized by unilateral attacks of severe pain accompanied by cranial autonomic features. Apart from these there are also sleep-related complaints and strong chronobiological features. The interaction between sleep and headache is complex at any level and evidence suggests that it may be of critical importance in our understanding of primary headache disorders. In cluster headache several interactions between sleep and the severe pain attacks have already been proposed. Supported by endocrinological and radiological findings as well as the chronobiological features, predominant theories revolve around central pathology of the hypothalamus. We aimed to investigate the clinical presentation of chronobiological features, the presence of concurrent sleep disorders and the relationship with particular sleep phases or phenomena, the possible role of hypocretin as well as the possible involvement of cardiac autonomic control. We conducted a questionnaire survey on 275 cluster headache patients and 145 controls as well an in-patient sleep study including 40 CH-patients and 25 healthy controls. The findings include: A distinct circannual connection between cluster occurrence and the amount of daylight, substantially poorer sleep quality in patients compared to controls which was present not only inside the clusters but also outside, affected REM-sleep in patients without a particular temporal connection to nocturnal attacks, equal prevalence of sleep apnea in both patient and control groups, reduced levels of hypocretin-1 in the cerebrospinal fluid of patients and finally a blunted response to the change from supine to tilted position in the head-up tilt table test indicating a weakened sympathoexcitatory or stronger parasympathetic drive. Overall, these findings support a theory of involvement of dysregulation in hypothalamic and brainstem nuclei in cluster headache pathology. Further, it is made plausible that the headache attacks are but one

  4. The Orion nebula star cluster

    NASA Technical Reports Server (NTRS)

    Panek, R. J.

    1982-01-01

    Photography through filters which suppress nebular light reveal a clustering of faint red stars centered on the Trapezium, this evidences a distinct cluster within the larger OB1 association. Stars within about 20 ft of trapezium comprise the Orion Nebula star cluster are considered. Topics discussed re: (1) extinction by dust grains; (2) photometric peculiarities; (3) spectroscopic peculiarities; (4) young variables; (5) the distribution and motion of gas within the cluster.

  5. Massive star clusters in galaxies.

    PubMed

    Harris, William E

    2010-02-28

    The ensemble of all star clusters in a galaxy constitutes its star cluster system. In this review, the focus of the discussion is on the ability of star clusters, particularly the systems of old massive globular clusters (GCs), to mark the early evolutionary history of galaxies. I review current themes and key findings in GC research, and highlight some of the outstanding questions that are emerging from recent work.

  6. moCluster: Identifying Joint Patterns Across Multiple Omics Data Sets.

    PubMed

    Meng, Chen; Helm, Dominic; Frejno, Martin; Kuster, Bernhard

    2016-03-04

    Increasingly, multiple omics approaches are being applied to understand the complexity of biological systems. Yet, computational approaches that enable the efficient integration of such data are not well developed. Here, we describe a novel algorithm, termed moCluster, which discovers joint patterns among multiple omics data. The method first employs a multiblock multivariate analysis to define a set of latent variables representing joint patterns across input data sets, which is further passed to an ordinary clustering algorithm in order to discover joint clusters. Using simulated data, we show that moCluster's performance is not compromised by issues present in iCluster/iCluster+ (notably, the nondeterministic solution) and that it operates 100× to 1000× faster than iCluster/iCluster+. We used moCluster to cluster proteomic and transcriptomic data from the NCI-60 cell line panel. The resulting cluster model revealed different phenotypes across cellular subtypes, such as doubling time and drug response. Applying moCluster to methylation, mRNA, and protein data from a large study on colorectal cancer patients identified four molecular subtypes, including one characterized by microsatellite instability and high expression of genes/proteins involved in immunity, such as PDL1, a target of multiple drugs currently in development. The other three subtypes have not been discovered before using single data sets, which clearly illustrates the molecular complexity of oncogenesis and the need for holistic, multidata analysis strategies.

  7. 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.

  8. 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.

  9. Equilibrium shapes of supported silver clusters

    NASA Astrophysics Data System (ADS)

    Stankic, Slavica; Cortes-Huerto, Robinson; Crivat, Nicoleta; Demaille, Dominique; Goniakowski, Jacek; Jupille, Jacques

    2013-02-01

    The morphology of silver nanoparticles supported on MgO smoke crystallites was studied by combining Transmission Electron Microscopy (TEM) and atomistic simulations of clusters of realistic size. Advantage was taken of the occurrence of well-defined complex MgO surfaces, including stepped surfaces and contact lines between stacked crystallites, to analyze Ag clusters of various orientations. Silver clusters were seen to adopt systematically the shape of a truncated octahedron irrespective of the support morphology. The (100)Ag//(100)MgO epitaxy was evidenced and (100), (111) and (110) facets were identified. The agreement between observed shapes and simulated profiles demonstrated that the formers were close to equilibrium which allowed the use of Wulff-Kaishew construction to determine the anisotropy ratios γ100/γ111 (1.03 +/- 0.03) and γ110/γ111 (1.08 +/- 0.03) and the Ag(100)/MgO(100) adhesion energy (0.58 +/- 0.10 J m-2) for clusters large enough to escape stress effects.

  10. Clusters and the new economics of competition.

    PubMed

    Porter, M E

    1998-01-01

    Economic geography in an era of global competition poses a paradox. In theory, location should no longer be a source of competitive advantage. Open global markets, rapid transportation, and high-speed communications should allow any company to source any thing from any place at any time. But in practice, Michael Porter demonstrates, location remains central to competition. Today's economic map of the world is characterized by what Porter calls clusters: critical masses in one place of linked industries and institutions--from suppliers to universities to government agencies--that enjoy unusual competitive success in a particular field. The most famous example are found in Silicon Valley and Hollywood, but clusters dot the world's landscape. Porter explains how clusters affect competition in three broad ways: first, by increasing the productivity of companies based in the area; second, by driving the direction and pace of innovation; and third, by stimulating the formation of new businesses within the cluster. Geographic, cultural, and institutional proximity provides companies with special access, closer relationships, better information, powerful incentives, and other advantages that are difficult to tap from a distance. The more complex, knowledge-based, and dynamic the world economy becomes, the more this is true. Competitive advantage lies increasingly in local things--knowledge, relationships, and motivation--that distant rivals cannot replicate. Porter challenges the conventional wisdom about how companies should be configured, how institutions such as universities can contribute to competitive success, and how governments can promote economic development and prosperity.

  11. Adaptive Clustering of Hypermedia Documents.

    ERIC Educational Resources Information Center

    Johnson, Andrew; Fotouhi, Farshad

    1996-01-01

    Discussion of hypermedia systems focuses on a comparison of two types of adaptive algorithm (genetic algorithm and neural network) in clustering hypermedia documents. These clusters allow the user to index into the nodes to find needed information more quickly, since clustering is "personalized" based on the user's paths rather than…

  12. Connecting Remote Clusters with ATM

    SciTech Connect

    Hu, T.C.; Wyckoff, P.S.

    1998-10-01

    Sandia's entry into utilizing clusters of networked workstations is called Computational Plant or CPlant for short. The design of CPlant uses Ethernet to boot the individual nodes, Myrinet to communicate within a node cluster, and ATM to connect between remote clusters. This SAND document covers the work done to enable the use of ATM on the CPlant nodes in the Fall of 1997.

  13. Stellar populations in star clusters

    NASA Astrophysics Data System (ADS)

    Li, Cheng-Yuan; de Grijs, Richard; Deng, Li-Cai

    2016-12-01

    Stellar populations contain the most important information about star cluster formation and evolution. Until several decades ago, star clusters were believed to be ideal laboratories for studies of simple stellar populations (SSPs). However, discoveries of multiple stellar populations in Galactic globular clusters have expanded our view on stellar populations in star clusters. They have simultaneously generated a number of controversies, particularly as to whether young star clusters may have the same origin as old globular clusters. In addition, extensive studies have revealed that the SSP scenario does not seem to hold for some intermediate-age and young star clusters either, thus making the origin of multiple stellar populations in star clusters even more complicated. Stellar population anomalies in numerous star clusters are well-documented, implying that the notion of star clusters as true SSPs faces serious challenges. In this review, we focus on stellar populations in massive clusters with different ages. We present the history and progress of research in this active field, as well as some of the most recent improvements, including observational results and scenarios that have been proposed to explain the observations. Although our current ability to determine the origin of multiple stellar populations in star clusters is unsatisfactory, we propose a number of promising projects that may contribute to a significantly improved understanding of this subject.

  14. 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).

  15. Iron-sulfur cluster biogenesis in mammalian cells: new insights into the molecular mechanisms of cluster delivery

    PubMed Central

    Maio, Nunziata; Rouault, Tracey. A.

    2014-01-01

    Iron-sulfur (Fe-S) clusters are ancient, ubiquitous cofactors composed of iron and inorganic sulfur. The combination of the chemical reactivity of iron and sulfur, together with many variations of cluster composition, oxidation states and protein environments, enables Fe-S clusters to participate in numerous biological processes. Fe-S clusters are essential to redox catalysis in nitrogen fixation, mitochondrial respiration and photosynthesis, to regulatory sensing in key metabolic pathways (i. e. cellular iron homeostasis and oxidative stress response), and to the replication and maintenance of the nuclear genome. Fe-S cluster biogenesis is a multistep process that involves a complex sequence of catalyzed protein- protein interactions and coupled conformational changes between the components of several dedicated multimeric complexes. Intensive studies of the assembly process have clarified key points in the biogenesis of Fe-S proteins. However several critical questions still remain, such as: what is the role of frataxin? Why do some defects of Fe-S cluster biogenesis cause mitochondrial iron overload? How are specific Fe-S recipient proteins recognized in the process of Fe-S transfer? This review focuses on the basic steps of Fe-S cluster biogenesis, drawing attention to recent advances achieved on the identification of molecular features that guide selection of specific subsets of nascent Fe-S recipients by the cochaperone HSC20. Additionally, it outlines the distinctive phenotypes of human diseases due to mutations in the components of the basic pathway. PMID:25245479

  16. Fractal polyzirconosiloxane cluster coatings

    SciTech Connect

    Sugama, T.

    1992-08-01

    Fractal polyzirconosiloxane (PZS) cluster films were prepared through the hydrolysis-polycondensation-pyrolysis synthesis of two-step HCl acid-NaOH base catalyzed sol precursors consisting of N-[3-(triethoxysilyl)propyl]-4,5-dihydroimidazole, Zr(OC{sub 3}H{sub 7}){sub 4}, methanol, and water. When amorphous PZSs were applied to aluminum as protective coatings against NaCl-induced corrosion, the effective film was that derived from the sol having a pH near the isoelectric point in the positive zeta potential region. The following four factors played an important role in assembling the protective PZS coating films: (1) a proper rate of condensation, (2) a moderate ratio of Si-O-Si to Si-O-Zr linkages formed in the PZS network, (3) hydrophobic characteristics, and (4) a specific microstructural geometry, in which large fractal clusters were linked together.

  17. Fractal polyzirconosiloxane cluster coatings

    SciTech Connect

    Sugama, T.

    1992-01-01

    Fractal polyzirconosiloxane (PZS) cluster films were prepared through the hydrolysis-polycondensation-pyrolysis synthesis of two-step HCl acid-NaOH base catalyzed sol precursors consisting of N-(3-(triethoxysilyl)propyl)-4,5-dihydroimidazole, Zr(OC{sub 3}H{sub 7}){sub 4}, methanol, and water. When amorphous PZSs were applied to aluminum as protective coatings against NaCl-induced corrosion, the effective film was that derived from the sol having a pH near the isoelectric point in the positive zeta potential region. The following four factors played an important role in assembling the protective PZS coating films: (1) a proper rate of condensation, (2) a moderate ratio of Si-O-Si to Si-O-Zr linkages formed in the PZS network, (3) hydrophobic characteristics, and (4) a specific microstructural geometry, in which large fractal clusters were linked together.

  18. Hydrated hydride anion clusters

    NASA Astrophysics Data System (ADS)

    Lee, Han Myoung; Kim, Dongwook; Singh, N. Jiten; Kołaski, Maciej; Kim, Kwang S.

    2007-10-01

    On the basis of density functional theory (DFT) and high level ab initio theory, we report the structures, binding energies, thermodynamic quantities, IR spectra, and electronic properties of the hydride anion hydrated by up to six water molecules. Ground state DFT molecular dynamics simulations (based on the Born-Oppenheimer potential surface) show that as the temperature increases, the surface-bound hydride anion changes to the internally bound structure. Car-Parrinello molecular dynamics simulations are also carried out for the spectral analysis of the monohydrated hydride. Excited-state ab initio molecular dynamics simulations show that the photoinduced charge-transfer-to-solvent phenomena are accompanied by the formation of the excess electron-water clusters and the detachment of the H radical from the clusters. The dynamics of the detachment process of a hydrogen radical upon the excitation is discussed.

  19. Clusters of Galaxies

    NASA Astrophysics Data System (ADS)

    Huchtmeier, W. K.; Richter, O. G.; Materne, J.

    1981-09-01

    The large-scale structure of the universe is dominated by clustering. Most galaxies seem to be members of pairs, groups, clusters, and superclusters. To that degree we are able to recognize a hierarchical structure of the universe. Our local group of galaxies (LG) is centred on two large spiral galaxies: the Andromeda nebula and our own galaxy. Three sr:naller galaxies - like M 33 - and at least 23 dwarf galaxies (KraanKorteweg and Tammann, 1979, Astronomische Nachrichten, 300, 181) can be found in the evironment of these two large galaxies. Neighbouring groups have comparable sizes (about 1 Mpc in extent) and comparable numbers of bright members. Small dwarf galaxies cannot at present be observed at great distances.

  20. Binaries in globular clusters

    NASA Technical Reports Server (NTRS)

    Hut, Piet; Mcmillan, Steve; Goodman, Jeremy; Mateo, Mario; Phinney, E. S.; Pryor, Carlton; Richer, Harvey B.; Verbunt, Frank; Weinberg, Martin

    1992-01-01

    Recent observations have shown that globular clusters contain a substantial number of binaries most of which are believed to be primordial. We discuss different successful optical search techniques, based on radial-velocity variables, photometric variables, and the positions of stars in the color-magnitude diagram. In addition, we review searches in other wavelengths, which have turned up low-mass X-ray binaries and more recently a variety of radio pulsars. On the theoretical side, we give an overview of the different physical mechanisms through which individual binaries evolve. We discuss the various simulation techniques which recently have been employed to study the effects of a primordial binary population, and the fascinating interplay between stellar evolution and stellar dynamics which drives globular-cluster evolution.