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

Levantamento estrutural da porção norte do Greenstone Belt do rio Itapicuru e dos Alvos Encantado e C1W, Bahia

The study area is located in the geological context of the northern portion of the Rio Itapicuru Greenstone Belt (GBRI), located northeast of the São Francisco Craton, Bahia State. The GBRI is known for its great economic potential for gold mineralization, looking south at Fazenda Brasileiro Mine and North Mine Maria Preta, is situated in the study área. The structural pattern of the northern portion of the Greenstone, theme of this work, is of great importance to understand the mineralization present. To characterize the structural model three geologic sections (scale 1:25000) were made with NW-SE and EW directions and detailing two mineralized targets, Encantado, located northwest of the area, near the city of Nordestina, and C1W, located near Itapicuru River, west of the Maria Preta mine. Thus, field work and petrographic analysis were conducted, that allow to indicate the existence of two structural domains characterized by the existence of a main foliation, low angle dipping main foliation and another with high dip angle, both with NW, moreover, folds occur in the area Dn-1 and post-Dn folds. Dn-1 folds are observed less frequently but they occur mainly forming an oblique foliation and the Sn is present in porphyroblasts observed in petrographic analysis, whereas in relation to the folds post Dn, there are more than one type of folding in area, which differ by the orientation of their axis, a post Dn NS and EW Dn another post. Moreover, two areas of metamorphic green schist (biotite zone) and medium amphibolite, which are directly related to the structural domains found

Caracterização mineralógica, petrológica e química da sulfetação nos reef's da mina Canavieiras, Jacobina, Bahia

In the Serra de Jacobina, localized in the North Central portion of the state of Bahia, occours the Jacobina Group. It’s a sedimentary basin and the gold deposit is stocked on the basal portion, which consist on quartzites intercalated with oligomítico metaconglomerates of Serra do Córrego Formation. There are controversies about the origin of the gold mineralization, but the currently most accepted hypothesis corresponds to a paleoplacer deposit with subsequent ore remobilization and concentration by hydrothermal process. The sulphidation is one of the main results of hydrothermal process, which was more detail characterized, besides identifying if there was more than one sulfides phase generation and its relationship with gold mineralization. The analyzes were performed from the main reef's (metaconglomerates mineralized levels) of Mine Canavieiras: Maneira, Holandez, Liberino, Piritoso, MU and LU. Chemical analyzes semi-quantitative were developed with EDS in MEV and also petrographics analyses. The main sulfide is pyrite, followed by chalcopyrite. Six groups of pyrite were classified according with chemical composition, however they show similarities in their habit and occurrence. Were identified four types of chlorite, labeled A, B, C, D. Gold occurs in free form, associate to pyrites, to Fe-Ti-Muscovite, to chlorite type B and to microfractures with iron hydroxide. Gold presents three different compositions: pure, with Ag or associated with U-Zr. The results of chemical analysis showed that the hydrothermal process have as their main source, ultramafic rocks present in the Jacobina Basin

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

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A importância da negatividade hegeliana para o pensamento dialético de Herbert Marcuse: o legado da filosofia da história

Pós-graduação em Filosofia - FFC

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)

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.

Magnetometric exploration in intrusive basic with evidence of gold in northern region of the Camaquã Sedimentary Basin (RS)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

The Myth of the Rational Market: Nudging Each Other Away from Fool’s Gold

A flurry of media commentary and several new books are focused on the recent financial crisis and near economic collapse. A Newsweek article by Zakaria (2009), “Greed is Good (To a Point),” suggests reconsidering the role of greed in capitalism. This is also the theme in Fools Gold (Tett, 2009), a story about the way derivatives markets have evolved: showing greed at its worst. In many ways this is the core source of the current set of problems. In some sense, these perspectives are integrated in The Myth of the Rational Market by Fox (2009), who traces the thinking on the efficient market hypothesis, now understood for what it is: a myth. Both books are based in large part on interviews with major players in the crisis. There are also books drawing mainly on science, but still quite accessible to general readers, as represented in Nudge by Thaler and Sunstein (2008). Both have done extensive research on human foibles in economic choice. There is also Animal Spirits (Akerlof and Schiller, 2009), a book about what Keynesian economics is really about, a look at human forces at work. Akerlof is a Nobel prize winner in economics, who before this has pointed to the problems with presuming rationality in real markets. Schiller is one of the few economists who predicted these events.