Self-assembly of organometallic Pd(II) complexes via CH3 center dot center dot center dot pi interactions: the first example of a cyclopalladated compound with herringbone stacking pattern

Two binuclear cyclometallated compounds [Pd(C-2,N-dmba)(mu-N-3)](2) (1) and [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] (2) (dmba = N,N-dimethylbenzylarnine) have been synthesized and characterized by elemental 3 analysis, IR and NMR spectroscopies and single crystal X-ray diffraction crystallography. The ability of CH3 groups to form C(sp(3))-H...pi hydrogen bonds with phenyl rings is responsible for the molecular self-assembly within the crystals of 1 and 2. Compound 1 crystallizes as one-dimensional supramolecular chains whereas the crystal packing of 2 consists of a herringbone of sandwiches composed by two inversely related [Pd-2(C-2,N-dmba)(2)(mu-N-3)(mu-Cl)] molecules. (c) 2007 Elsevier B.V. All rights reserved.

Self-assembly of Pd(II) pyrazolyl complexes to 1-D hydrogen-bonded coordination polymers

This work describes the synthesis and characterization of two novel Pd(II) pyrazolyl complexes of the type [PdX2(HdmPz)(2)](n) {X=SCN- (1), N-3(-) (2); HdmPz=3,5-dimethylpyrazole} that self-assemble through N-H...NCS or N-H...NNN hydrogen bonds to yield infinite one-dimensional chains, as confirmed by single crystal X-ray study on 1. The expected solid state polymeric structure for 2 is slowly broken up in CHCl3 Solution, leading to an equilibrium mixture of cis and trans-[Pd(N-3)(2)(HdmPz)(2)] monomers, as demonstrated by time-dependent IR and NMR studies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Surface effects on moving vortices in superconducting stripes

Size and surface dynamical effects are investigated in thin superconducting stripes with variable width. We perform numerical simulations of the vortex dynamics, with the inclusion of the surface confining potential and a random distribution of pinning centers. To fully characterize the vortex flow, we calculate the differential resistance, the transverse diffusion coefficient, the structure factor and the intensity of the Bragg peaks, as functions of the transport force. We found that surface effects induce a premature ordering of the flux line lattice, and the system displays plastic and smectic behavior only in a very narrow range of forces. (c) 2007 Elsevier B.V. All rights reserved.

Low-weight coordination polymers derived from the self-assembly reactions of Pd(II) pyrazolyl compounds and azide ion

The low-weight Pd(II) coordination polymers [(N(3))(HL)Pd {Pd(3)(mu-N(3))(mu-L)(5)}10(mu-L)(2)Pd(L)(HL)]{L = Pz(-) (1); mPz(-) (2), IPz(-)(3)} and [(N(3))(HPz)Pd{Pd(6)(mu-N(3))(2)(mu-PZ)(5)(mu-L)(5)}(10)(mu-L)(2)Pd(Pz)(HPz)] {L = mPz(-) (4), dmPz(-) (5); IPz(-) (6)} {L = pyrazolate (Pz(-)), 4-methylpyrazolate(mPz(-)), 4-iodopyrazo late (IPz(-)), 3,5-dimethylpyrazolate (dmPz(-))} have been prepared in this work. IR spectra clearly indicated the exobidentate nature of pyrazolato ligands as well the end-on coordination mode of the azido group. The molecular weight determinations by osmometry indicated that the species have a low degree of polymerization (n = 10). NMR experiments showed two pyrazolate environments in a 2:1 ratio, being assigned to the six-membered ring Pd(mu-L)(2)Pd and the Pd(mu-N(3))(mu-L)Pd metallocycle, respectively. UV-visible spectroscopy gave further evidences for the oligomeric structures of 1-6. Some alternative structures for the isostructural polymers have been suggested. (c) 2005 Elsevier Ltd. All rights reserved.

Effects of self-assembly process of latex spheres on the final topology of macroporous silica

This paper surveys the topology of macroporous silica prepared using latex templates covering the submicrometric range (0.1-0.7 mu m). The behavior of latex spheres in aqueous dispersion has been analyzed by dynamic light scattering (DLS) measurement indicating the most appropriate conditions to form well-defined cubic arrays. The optical behavior of latex spheres has been analyzed by transmittance and reflectance measurements in order to determine their diameter and filling factor when they were assembled in bidimensional arrays. Macroscopic templates have been obtained by a centrifugation process and their crystalline ordering has been confirmed by porosimetry and scanning electron microscopy. These self-assembled structures have been used to produce macroporous silica, whose final topology depends on the pore size distribution of the original template. It has been seen that latex spheres are ordered in a predominant fcc arrangement with slipping of tetragonal pores due to the action of attractive electrostatic interactions. The main effect is to change the spherical shape of voids in macroporous silica into a hexagonal configuration with possible applications to fabricate photonic devices with novel optical properties. (c) 2005 Elsevier B.V. All rights reserved.

Dinuclear Azide-Bridged Copper(II) Complex as Building Block for the Assembly of a 2D-Supramolecular Array

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Hierarchical Assembly of CaMoO4 Nano-Octahedrons and Their Photoluminescence Properties

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Simple heuristics for the assembly line worker assignment and balancing problem

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Inorganic-Organic Nanocomposite Assembly Using Collagen as a Template and Sodium Tripolyphosphate as a Biomimetic Analog of Matrix Phosphoprotein

Nanocomposites created with polycarboxylic acid alone as a stabilization agent for prenucleation clusters-derived amorphous calcium phosphate exhibit nonperiodic apatite deposition. In the present study, we report the use of inorganic polyphosphate as a biomimetic analog of matrix phosphoprotein for directing poly(acrylic acid)-stabilized amorphous nano-precursor phases to assemble into periodic apatite-collagen nanocomposites. The sorption and desorption characteristics of sodium tripolyphosphate to type I collagen were examined. Periodic nanocomposite assembly with collagen as a template was demonstrated with TEM and SEM using a Portland cement-based resin composite and a phosphate-containing simulated body fluid. Apatite was detected within the collagen at 24 h and became more distinct at 48 h, with prenucleation clusters attaching to the collagen fibril surface during the initial infiltration stage. Apatite-collagen nanocomposites at 72 h were heavily mineralized with periodically arranged intrafibrillar apatite platelets. Defect-containing nanocomposites caused by desorption of TPP from collagen fibrils were observed in regions lacking the inorganic phase.

Neoproterozoic tectonic and magmatic episodes in the NW sector of Borborema Province, NE Brazil, during assembly of Western Gondwana

The Medio Coreau domain of NE Brazil is located along the northwest margin of Borborema Province, the western branch of a Brasiliano/Pan-African collisional belt that formed during the assembly of Western Gondwana. The early Paleoproterozoic basement of the Medio Coreau domain is composed of migmatitic gneisses and juvenile granulites, overlain by late Paleoproterozoic and Neoproterozoic rocks intruded by syn- to post-tectonic Brasiliano granitoids. According to integrated structural and geochronological data (U-Pb zircon and monazite ages), the Neoproterozoic tectonic evolution of the Medio Coreau is characterized by low-angle thrusting and transcurrent deformation. U-Pb geochronological data from plutons intruded during this compressional regime indicate the collisional evolution began at approximately 622 Ma and continued until about 591 Ma. The continuation of convergence until approximately 560 Ma resulted in the formation of NE-SW and E-W shear zones within the Borborema Province and adjoining West African provinces. The final stage of the ductile tectonism was characterized by uplift and high-angle fault generation between approximately 560 and 545 Ma. The last tectonic event was an extensional phase, resulting in the formation of the Jaibaras graben and intrusion of post-orogenic granites at around 532 Ma. (c) 2007 Elsevier Ltd. All rights reserved.

On the riddle of the moving thermometers

The assumption that equilibrium is a Lorentz invariant notion, associated with the measurements of the earth's velocity with respect to the cosmic microwave background, strongly suggest that the temperature of a system seen from a moving frame is higher than the temperature seen from the rest frame. © 1992.

Evidence for Neoproterozoic continental arc magmatism in the Santa Quitéria Batholith of Ceará State, NW Borborema Province, NE Brazil: Implications for the assembly of West Gondwana

Recent field investigations and geochronological studies of Neoproterozoic rocks in the northwestern part of the Borborema Province, Ceará State, NE Brazil provide important clues pertaining to the nature of convergence between the Borborema Province and the West African-São Luis craton during the assembly of West Gondwana. U-Pb zircon data indicate that the earliest evidence of convergent magmatism along the northwest margin of the Borborema Province occurred around 777 Ma, and was followed by the development of a large continental arc batholith (Santa Quitéria batholith) between ca. 665 and 591 Ma within the central part of Ceará State. These findings, along with supporting geophysical data, suggest that convergence between the Borborema Province and the West African-São Luis craton involved closure of an oceanic realm with subduction polarity to the southeast beneath the northwestern part of the province. Consequently, it seems likely that the Pharusian Ocean was continuous from the Hoggar Province in West Africa into South America during the late Neoproterozoic and additional data suggests that it may have even been connected with the Goianides Ocean of the Brasília Belt farther to the southwest.

U-Pb geochronology of the southern Brasília belt (SE-Brazil): Sedimentary provenance, Neoproterozoic orogeny and assembly of West Gondwana

The Brasília belt borders the western margin of the São Francisco Craton and records the history of ocean opening and closing related to the formation of West Gondwana. This study reports new U-Pb data from the southern sector of the belt in order to provide temporal limits for the deposition and ages of provenance of sediments accumulated in passive margin successions around the south and southwestern margins of the São Francisco Craton, and date the orogenic events leading to the amalgamation of West Gondwana. Ages of detrital zircons (by ID-TIMS and LA-MC-ICPMS) were obtained from metasedimentary units of the passive margin of the São Francisco Craton from the main tectonic domains of the belt: the internal allochthons (Araxá Group in the Áraxá and Passos Nappes), the external allochthons (Canastra Group, Serra da Boa Esperança Metasedimentary Sequence and Andrelândia Group) and the autochthonous or Cratonic Domain (Andrelândia Group). The patterns of provenance ages for these units are uniform and are characterised as follows: Archean- Paleoproterozoic ages (3.4-3.3, 3.1-2.7, and 2.5-2.4Ga); Paleoproterozoic ages attributed to the Transamazonian event (2.3-1.9Ga, with a peak at ca. 2.15Ga) and to the ca. 1.75Ga Espinhaço rifting of the São Francisco Craton; ages between 1.6 and 1.2Ga, with a peak at 1.3Ga, revealing an unexpected variety of Mesoproterozoic sources, still undetected in the São Francisco Craton; and ages between 0.9 and 1.0Ga related to the rifting event that led to the individualisation of the São Francisco paleo-continent and formation of its passive margins. An amphibolite intercalation in the Araxá Group yields a rutile age of ca. 0.9Ga and documents the occurrence of mafic magmatism coeval with sedimentation in the marginal basin. Detrital zircons from the autochthonous and parautochthonous Andrelândia Group, deposited on the southern margin of the São Francisco Craton, yielded a provenance pattern similar to that of the allochthonous units. This result implies that 1.6-1.2Ga source rocks must be present in the São Francisco Craton. They could be located either in the cratonic area, which is mostly covered by the Neoproterozoic epicontinental deposits of the Bambuí Group, or in the outer paleo-continental margin, buried under the allochthonous units of the Brasília belt. Crustal melting and generation of syntectonic crustal granites and migmatisation at ca. 630Ma mark the orogenic event that started with westward subduction of the São Francisco plate and ended with continental collision against the Paraná block (and Goiás terrane). Continuing collision led to the exhumation and cooling of the Araxá and Passos metamorphic nappes, as indicated by monazite ages of ca. 605Ma and mark the final stages of tectonometamorphic activity in the southern Brasília belt. Whilst continent-continent collision was proceeding on the western margin of the São Francisco Craton along the southern Brasília belt, eastward subduction in the East was generating the 634-599Ma Rio Negro magmatic arc which collided with the eastern São Francisco margin at 595-560Ma, much later than in the Brasília belt. Thus, the tectonic effects of the Ribeira belt reached the southernmost sector of the Brasília belt creating a zone of superposition. The thermal front of this event affected the proximal Andrelândia Group at ca. 588Ma, as indicated by monazite age. The participation of the Amazonian craton in the assembly of western Gondwana occurred at 545-500Ma in the Paraguay belt and ca. 500Ma in the Araguaia belt. This, together with the results presented in this work lead to the conclusion that the collision between the Paraná block and Goiás terrane with the São Francisco Craton along the Brasília belt preceded the accretion of the Amazonian craton by 50-100 million years. © 2003 Elsevier B.V. All rights reserved.

Transforming open mining pits into fish farms: Moving towards sustainability

The legacy of mining activities has typically been land 'returned to wildlife', or, at some sites, degraded to such an extent that it is unsuitable for any alternate use. Progress towards sustainability is made when value is added in terms of the ecological, social and economic well-being of the community. In keeping with the principles of sustainable development, the innovative use of flooded open pits and tailings impoundments as commercial, recreational or ornamental fish farms should be considered in some locations, as it could make a significant contribution to the social equity, economic vitality and environmental integrity of mining communities. This article highlights the growing significance of aquaculture and explores the benefits and barriers to transforming flooded pits and impoundments into aquaculture operations. Among other benefits, aquaculture may provide a much-needed source of revenue, employment and, in some cases, food to communities impacted by mine closure. Further, aquaculture in a controlled closed environment may be more acceptable to critics of fish farming who are concerned about fish escapes and viral transmissions to wild populations. Despite the potential benefits, aquaculture in flooded pits and impoundments is not without its complications - it requires a site-specific design approach that must consider issues ranging from metals uptake by fish, to the long-term viability of the aquatic system as fish habitat, to the overall contribution of aquaculture to sustainability. © 2004 United Nations. Published by Blackwell Publishing.