Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

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

Stretching of BDT-gold molecular junctions: thiol or thiolate termination?

It is often assumed that the hydrogen atoms in the thiol groups of a benzene-1,4-dithiol dissociate when Au-benzene-1,4-dithiol-Au junctions are formed. We demonstrate, by stability and transport property calculations, that this assumption cannot be made. We show that the dissociative adsorption of methanethiol and benzene-1,4-dithiol molecules on a flat Au(111) surface is energetically unfavorable and that the activation barrier for this reaction is as high as 1 eV. For the molecule in the junction, our results show, for all electrode geometries studied, that the thiol junctions are energetically more stable than their thiolate counterparts. Due to the fact that density functional theory (DFT) within the local density approximation (LDA) underestimates the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital by several electron-volts, and that it does not capture the renormalization of the energy levels due to the image charge effect, the conductance of the Au-benzene-1,4-dithiol-Au junctions is overestimated. After taking into account corrections due to image charge effects by means of constrained-DFT calculations and electrostatic classical models, we apply a scissor operator to correct the DFT energy level positions, and calculate the transport properties of the thiol and thiolate molecular junctions as a function of the electrode separation. For the thiol junctions, we show that the conductance decreases as the electrode separation increases, whereas the opposite trend is found for the thiolate junctions. Both behaviors have been observed in experiments, therefore pointing to the possible coexistence of both thiol and thiolate junctions. Moreover, the corrected conductance values, for both thiol and thiolate, are up to two orders of magnitude smaller than those calculated with DFT-LDA. This brings the theoretical results in quantitatively good agreement with experimental data.

Modelo estrutural do maciço rochoso do Depósito de Cobre e Ouro da Mina da Chapada, Alto Horizonte, GO

The Cu-Au mine of Chapada is located in the municipality of Alto Horizonte, in the northwestern portion of Goiás state and is inserted in the geological context of the Brasilia Belt, specifically the Mara Rosa Magmatic Arc, which hosts important deposits of Au and Cu-Au. The rocks found in the study area belong mainly to the Volcano-Sedimentary Sequence of Mara Rosa and are composed of basic to acidic metavolcanic rocks, psammiticpellitic metasedimentary rocks, chemical rocks and also hydrothermal products. Late intrusions occur and are represented by pegmatitic dikes and tonalitic bodies. The ore deposit of the Chapada mine is formed predominantly by the chalcopyrite-pyritemagnetite association, where pyrite is the most abundant mineral. Through the structural mapping of the mining fronts, it was able to recognize three deformational phases (Dn, Dn +1, Dn +2). During the Dn phase, isoclinal recumbent folds were formed, in association with amphibolites facies metamorphism. Later, in phase Dn +1, there was formation of drag folds and intrafolial folds in association with retrograde metamorphism in the greenschist facies. The deformational phase Dn +2, in its turn, was responsible for late symmetrical folding of the foliation, with NS and EW axes, resulting in an interference pattern of the dome-and-basin type

Geologia do depósito de ouro do alvo guarda-mor, na sequência Jaupaci (Israelândia - GO)

The study area of the Guarda-Mor target (Israelândia-GO) contextualizes the terrains of the estaern portion of the Arenópolis Magmatic Arc, more accurately, the Neoproterozoic associations inserted in the field of the Jaupaci volcano-sedimentary sequence. The mapped area is located in the central-western of Goiás state. The presente paper has as main objective to characterize the structural, petrographic and litogeochemistry of the target rocks beyond to compare these factors with the Mina Bacilândia rocks (Fazenda Nova-GO) in order to assess the genetic similarity of volcano-sedimentary units and deposits associated. The Guarda-Mor target is represented by the Jaupaci metavolcanic rocks sequence presenting bimodal volcanism. This sequence consists in metafelsic rocks like sericite/muscovite quartz schist, phyllite and metarriolites and/or metariodacites with calc-alkaline geochemical signature and metamafic rocks with tholeiitic character formed by actinolite - chlorite schist and chlorite - quartz schist. Besides the package of supracrustal rocks also can be observed the occurrence of a local intrusion syn- to late - tectonic named Granito Subvulcânico. In the study area beyond the marked volcanism also seen an event of crustal melting granitogênese evidenced by the presence of 2 granites at the east and the west of the map, Granito Israelândia and Granito Iporá respectively. Structural analysis both at the macro and micro have identified 3 deformation phases. The types of rock on the region record features in the metamorphic facies top and down. These features were subdivided into 3 metamorphic areas: the east and West areas show thermal metamorphism due to intrusion of adjacente granites while the central domain displays features of regional metamorphism. Gold mineralization of the Guarda –Mor deposit target suggests a possible structural control beyond pronounced the hydrothermal alteration. The mineralization may also be...

Análise estrutural e microtectônica da inflexão do jordino e depósitos de ouro associados no greenstone belt de Pilar de Goiás

The study area is included in the geological context of the Goias Median Massif, a region where there are associations of Archean granite-gneiss complex (Block Moquém) and a Paleoproterozoic metavolcano-sedimentary sequence ( Pilar greenstone belt ). At the south of area, the greenstone sequence is partially overlain by Neopreoterozoic metasediments of the Araxá Group. The lithostratigraphic units of the Pilar greenstone belt define a shift from about N30W direction (north of the deposit) to N60 and 70W in the region south of the Jordino deposit, where are truncated by the Araxá Group rocks. Mineralogical associations described in this paper allow to indicate that the regional metamorphism that affected the rocks of the greenstone belt and Araxá Group, in the mapped area, reached the upper greenschist facies (garnet zone). Data obtained during mapping and by microtectonics analysis allow to indicate the existence of at least four deformational events that acted on the rocks of the Guarinos greenstone belt and Araxá Group, represented by the phases called Dn-1, Dn, Dn + 1 and Dn+2. It was observed that the pattern of sulphide porfitoblasts in mineralized levels is similar to garnet, biotite and muscovite porfiroblasts (tardi to post Dn) that marks the metamorphic peak of the area

Indirect doping of microstructures fabricated by two-photon polymerization with gold nanoparticles

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Elementos estruturais relacionados com a mineralização do eoceno - oligoceno entre Mollebamba e Santo Domingo região de Apurimac, sul do Peru

Pós-graduação em Geociências e Meio Ambiente - IGCE

Enhanced Mechanical Stability of Gold Nanotips through Carbon Nanocone Encapsulation

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Orange pectin mediated growth and stability of aqueous gold and silver nanocolloids

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

A flexible lab-on-a-chip for the synthesis and magnetic separation of magnetite decorated with gold nanoparticles

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

Ultramafic complexes and associated mineral deposits in the Precambrian of eastern Minas Gerais, Brazil

Based on field work, prospection and petrographic studies ultramafic complexes and their mineral deposits from eastern Minas Gerais in southeastern Brazil are generally outlined to form a basis for future investigations in this region. The bodies dealt with occur at Ipanema, Córrego Novo, Bela Vista de Minas, Rio Pomba and Liberdade. These ultramafic bodies are generally enclosed in high-grade gneisses and consist of serpentinized peridotites and harzburgites which were metamorphosed together with their country rocks in upper amphibolite to granulite facies. Weathering of these rocks gives rise to nickeliferous laterite, while metamorphism has resulted in anthophyllite asbestos and talc deposits. © 1985 Springer-Verlag.

Gold electrodes from recordable CDs for mercury quantification by flow injection analysis

The development of a new methodology for the construction of very efficient flow cells for mercury detection by potentiometric stripping analysis, employing the thin gold layer of recordable CDs as working electrode is reported. This new source of electrodes (CDtrodes) show very attractive performance, similar to that obtained with commercial gold electrodes, with superior versatility. The low cost of this new source of gold electrodes allows a frequent replacement of the electrode, avoiding cumbersome clean-up treatments. Various experimental parameters have been optimized to yield low detection limits (0.25 ng/mL of mercury for 5 min deposition at 0.3 V) and good precision (standard deviation of 1.9% was obtained for 15 repetitive measurements using 10 ng/mL of mercury). Standard curves were found to be linear over the range of 0.5-100 μg L-1 of mercury. The flow cells developed were used for the quantification of mercury in oceanic and tap water. © Springer-Verlag 2000.

Is bone transplantation the gold standard for repair of alveolar bone defects?

New strategies to fulfill craniofacial bone defects have gained attention in recent years due to the morbidity of autologous bone graft harvesting. We aimed to evaluate the in vivo efficacy of bone tissue engineering strategy using mesenchymal stem cells associated with two matrices (bovine bone mineral and α-tricalcium phosphate), compared to an autologous bone transfer. A total of 28 adult, male, non-immunosuppressed Wistar rats underwent a critical-sized osseous defect of 5 mm diameter in the alveolar region. Animals were divided into five groups. Group 1 (n = 7) defects were repaired with autogenous bone grafts; Group 2 (n = 5) defects were repaired with bovine bone mineral free of cells; Group 3 (n = 5) defects were repaired with bovine bone mineral loaded with mesenchymal stem cells; Group 4 (n = 5) defects were repaired with α-tricalcium phosphate free of cells; and Group 5 (n = 6) defects were repaired with α-tricalcium phosphate loaded with mesenchymal stem cells. Groups 2-5 were compared to Group 1, the reference group. Healing response was evaluated by histomorphometry and computerized tomography. Histomorphometrically, Group 1 showed 60.27% ± 16.13% of bone in the defect. Groups 2 and 3 showed 23.02% ± 8.6% (p = 0.01) and 38.35% ± 19.59% (p = 0.06) of bone in the defect, respectively. Groups 4 and 5 showed 51.48% ± 11.7% (p = 0.30) and 61.80% ± 2.14% (p = 0.88) of bone in the defect, respectively. Animals whose bone defects were repaired with α-tricalcium phosphate and mesenchymal stem cells presented the highest bone volume filling the defects; both were not statistically different from autogenous bone.

Co-deposition of gold nanoparticles and metalloporphyrin using the langmuir-blodgett (LB) technique for Surface-Enhanced Raman Scattering (SERS)

The synergistic effect produced by metallic nanoparticles when incorporated into different systems empowers a research field that is growing rapidly. In addition, organometallic materials are at the center of intensive research with diverse applications such as light-emitting devices, transistors, solar cells, and sensors. The Langmuir-Blodgett (LB) technique has proven to be suitable to address challenges inherent to organic devices, since the film properties can be tuned at the molecular level. Here we report a strategy to incorporate gold nanoparticles (AuNPs) into the LB film by co-deposition in order to achieve surface-enhanced Raman scattering (SERS) of the zinc(II)-protoporphyrin (IX) dimethyl ester (ZnPPIX-DME). Prior to the LB co-deposition, the properties of the Langmuir monolayer of ZnPPIX-DME at the air-water interface, containing AuNPs in the subphase, are studied through the surface-pressure versus mean molecular area (π-A) isotherms. The ZnPPIX-DME+AuNPs π-A isotherm presented a significant shift to higher molecular area, suggesting an interaction between both ZnPPIX-DME molecules and AuNPs. Those interactions are a key factor allowing the co-deposition of both AuNPs and ZnPPIX-DME molecules onto a solid substrate, thus forming the LB film. SERS of ZnPPIX-DME was successfully attained, ensuring the spatial distribution of the AuNPs. Higher enhancement factors were found at AuNP aggregates, as a result of the intense local electromagnetic field found in the metal nanoparticle aggregates. The main vibrational bands observed in the SERS spectra suggest a physical adsorption of the ZnPPIX-DME onto the surface of AuNPs. The latter is not only in agreement with the interactions pointed out by the π-A isotherms but also suggests that this interaction is kept upon LB film co-deposition.