Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.

Synthesis and Characterization of Gold/Alanine Nanocomposites with Potential Properties for Medical Application as Radiation Sensors

Radiation dose assessment is essential for several medical treatments and diagnostic procedures. In this context, nanotechnology has been used in the development of improved radiation sensors, with higher sensitivity as well as smaller sizes and energy dependence. This paper deals with the synthesis and characterization of gold/alanine nanocomposites with varying mass percentage of gold, for application as radiation sensors. Alanine is an excellent stabilizing agent for gold nanoparticles because the size of the nanoparticles does not augment with increasing mass percentage of gold, as evidenced by UV-vis spectroscopy, dynamic light scattering, and transmission electron microscopy. X-ray diffraction patterns suggest that the alanine crystalline orientation undergoes alterations upon the addition of gold nanoparticles. Fourier transform infrared spectroscopy indicates that there is interaction between the gold nanoparticles and the amine group of the alanine molecules, which may be the reason for the enhanced stability of the nanocomposite. The application of the nanocomposites as radiation detectors was evaluated by the electron spin resonance technique. The sensitivity is improved almost 3 times in the case of the nanocomposite containing 3% (w/w) gold, so it can be easily tuned by changing the amount of gold nanoparticles in the nanocomposites, without the size of the nanoparticles influencing the radiation absorption. In conclusion, the featured properties, such as homogeneity, nanoparticle size stability, and enhanced sensitivity, make these nanocomposites potential candidates for the construction of small-sized radiation sensors with tunable sensitivity for application in several medical procedures.

Conical crowns with electroplated gold copings: retention force changes caused by wear and combined off-axial load

The aim of this study was to examine the wear behavior of conical crowns of gold alloy and zirconium dioxide ceramics facing electroplated gold copings.

Vapor bubble generation around gold nano-particles and its application to damaging of cells

We investigated vapor bubbles generated upon irradiation of gold nanoparticles with nanosecond laser pulses. Bubble formation was studied both with optical and acoustic means on supported single gold nanoparticles and single nanoparticles in suspension. Formation thresholds determined at different wavelengths indicate a bubble formation efficiency increasing with the irradiation wavelength. Vapor bubble generation in Bac-1 cells containing accumulations of the same particles was also investigated at different wavelengths. Similarly, they showed an increasing cell damage efficiency for longer wavelengths. Vapor bubbles generated by single laser pulses were about half the cell size when inducing acute damage.

Changes in retention force with electroplated copings on conical crowns: a comparison of gold and zirconia primary crowns

The aim of this study was to examine the wear behavior of conical crowns with electroplated gold copings that are used to connect implants and teeth to a removable denture. Gold alloy and zirconium dioxide ceramic crowns were compared.

THERMORESPONSIVE PROPERTIES OF GOLD HYBRID NANOPARTICLES OF POLY(DI(ETHYLENE GLYCOL) METHYL ETHER METHACRYLATE) (PDEGMA) AND ITS BLOCK COPOLYMERS WITH DIFFERENT ANCHORING REGIMES

Thermo-responsive materials have been of interest for many years, and have been studied mostly as thermally stimulated drug delivery vehicles. Recently acrylate and methacrylates with pendant ethylene glycol methyl ethers been studied as thermo responsive materials. This work explores thermo response properties of hybrid nanoparticles of one of these methacrylates (DEGMA) and a block copolymer with one of the acrylates (OEGA), with gold nanoparticle cores of different sizes. We were interested in the effects of gold core size, number and type of end groups that anchored the chains to the gold cores, and location of bonding sites on the thermo-response of the polymer. To control the number and location of anchoring groups we using a type of controlled radical polymerization called Reversible Addition Fragmentation Transfer (RAFT) Polymerization. Smaller gold cores did not show the thermo responsive behavior of the polymer but the gold cores did seem to self-assemble. Polymer anchored to larger gold cores did show thermo responsivity. The anchoring end group did not alter the thermoresponsivity but thiol-modified polymers stabilized gold cores less well than chains anchored by dithioester groups, allowing gold cores to grow larger. Use of multiple bonding groups stabilized the gold core. Using block copolymers we tested the effects of number of thiol groups and the distance between them. We observed that the use of multiple anchoring groups on the block copolymer with a sufficiently large gold core did not prevent thermo responsive behavior of the polymer to be detected which allows a new type of thermo-responsive hybrid nanoparticle to be used and studied for new applications.

Evaluating the relationship between moisture induced expansion and horizontal stress orientation in samples from the nonesuch formation

High horizontal stresses can cause numerous ground control problems in mines and other underground structures ultimately impacting worker safety, productivity and the economics of an underground operation. Mine layout and design can be optimized when the presence and orientation of these stresses are recognized and their impact minimized. A simple technique for correlating the principal horizontal stress direction in a sedimentary rock mass with the preferential orientation of moisture induced expansion in a sample of the same rock was introduced in the 1970s and has since gone un-reported and unused. This procedure was reexamined at a locality near the original test site at White Pine, Michigan in order to validate the original research and to consider its usefulness in mining and civil engineering applications in high horizontal stress conditions. This procedure may also be useful as an economical means for characterizing regional stress fields.

"Brethren upon the same level" : membership and class in Calumet's Masonic Lodge

The Keweenaw Peninsula of Upper Michigan was a ethnic conglomerate of cultures and ideas, with people attracted to the area by the mineral wealth found along the Copper Range. The center of copper mining from the mid 1860s to 1968 was in the vicinity of Calumet Township, home to the world-famous Calumet and Hecla Mining Company. The township depended on the mines and the company’s president Agassiz’s strove to make the area a “model community,” that included groups such as the Free and Accepted Masons. Men from myriad backgrounds arrived in Calumet from the British Isles, Germany, Finland, Eastern and Southern Europe and the Eastern United States. As in other communities from the time period these men formed common interest groups like Masonic Lodge 271, which received its charter in 1870. Gentlemen joined with merchants and craftsmen. They became “brethren upon the same level,” and were elevated to the status of Master Mason. This symbolic transformation within the Lodge removed the men from the “profane world” outside the sanctity of Masonry, and in the ritualistic transformation of the meeting they were reborn into Masonry’s sacred mysteries. Masonry acted as a means of moral guidance to men and gave them access to a larger social and economic community through a common connection of brotherhood. As the candidates moved through the three Blue Lodge degrees of Entered Apprentice, Fellowcraft, and Master Mason they saw each other as “brethren upon the same level” – all economic classes equal within the Masonic Lodge. To examine equality within Lodge 271, this study sorted workers into classes to allow a comparison of Lodge 271’s membership. Possibly a comparison between other lodges can be drawn from the membership. The Union Building in Calumet, MI will be examined for its role in the ritualistic transformation of Masonry as it housed Masonic activities and transformations. This transformation brought men into the lodge of brothers. While Masonry professed equality between members however, to what extent did the membership of the lodge reflect this between the brethren? To what extent did economic class determine who was made “brethren upon the same level? 1 Arthur Thurner, Calumet Copper and People: History of a Michigan Mining Community, 1864-1970 (Hancock, MI: Book Concern, 1974), 122.

Geochemistry and Stable Isotopes of Surface Water and Groundwater in the Continental Pit in Butte, Montana, USA

The Continental porphyry Cu‐Mo mine, located 2 km east of the famous Berkeley Pit lake of Butte, Montana, contains two small lakes that vary in size depending on mining activity. In contrast to the acidic Berkeley Pit lake, the Continental Pit waters have near-neutral pH and relatively low metal concentrations. The main reason is geological: whereas the Berkeley Pit mined highly‐altered granite rich in pyrite with no neutralizing potential, the Continental Pit is mining weakly‐altered granite with lower pyrite concentrations and up to 1‐2% hydrothermal calcite. The purpose of this study was to gather and interpret information that bears on the chemistry of surface water and groundwater in the active Continental Pit. Pre‐existing chemistry data from sampling of the Continental Pit were compiled from the Montana Bureau of Mines and Geology and Montana Department of Environmental Quality records. In addition, in March of 2013, new water samples were collected from the mine’s main dewatering well, the Sarsfield well, and a nearby acidic seep (Pavilion Seep) and analyzed for trace metals and several stable isotopes, including dD and d18O of water, d13C of dissolved inorganic carbon, and d34S of dissolved sulfate. In December 2013, several soil samples were collected from the shore of the frozen pit lake and surrounding area. The soil samples were analyzed using X‐ray diffraction to determine mineral content. Based on Visual Minteq modeling, water in the Continental Pit lake is near equilibrium with a number of carbonate, sulfate, and molybdate minerals, including calcite, dolomite, rhodochrosite (MnCO3), brochantite (CuSO4·3Cu(OH)2), malachite (Cu2CO3(OH)2), hydrozincite (Zn5(CO3)2(OH)6), gypsum, and powellite (CaMoO4). The fact that these minerals are close to equilibrium suggests that they are present on the weathered mine walls and/or in the sediment of the surface water ponds. X‐Ray Diffraction (XRD) analysis of the pond “beach” sample failed to show any discrete metal‐bearing phases. One of the soil samples collected higher in the mine, near an area of active weathering of chalcocite‐rich ore, contained over 50% chalcanthite (CuSO4·5H2O). This water‐soluble copper salt is easily dissolved in water, and is probably a major source of copper to the pond and underlying groundwater system. However, concentrations of copper in the latter are probably controlled by other, less‐soluble minerals, such as brochantite or malachite. Although the acidity of the Pavilion Seep is high (~ 11 meq/L), the flow is much less than the Sarsfield Well at the current time. Thus, the pH, major and minor element chemistry in the Continental Pit lakes are buffered by calcite and other carbonate minerals. For the Continental Pit waters to become acidic, the influx of acidic seepage (e.g., Pavilion Seep) would need to increase substantially over its present volume.

Geology of Upper Bear Gulch and Dry Boulder Creek Area Madison County, Montana

Potential gold mines lie high among the rugged peaks of the Tobacco Root Mountains of southwestern Montana. This is a region where little geologic work has been done, though extensive mine operations have been carried on, and valuable ore has been shipped.

Geological and geochemical characteristics of the Tersang gold deposit, Malaysia: implications for genesis and gold exploration

The Central gold belt of peninsular Malaysia comprises a number of gold deposits located in the east of the N-S striking Bentong-Raub Suture Zone. The Tersang gold deposit is one of the gold deposits in the gold belt and hosted in sandstone, rhyolite and breccia units. The deposit has an inferred resource of 528,000 ounces of gold. The geochronology of the Tersang deposit has been newly constrained by LA ICP-MS U-Pb zircon dating. The maximum depositional age of the host sedimentary rocks ranges from Early Carboniferous to Early Permian (261.5 ± 4.9 Ma to 333.5 ± 2.5 Ma) for the host sandstone and Late Triassic for the rhyolite intrusion (218.8 ± 1.7 Ma). Textural characteristics of pyrite have revealed five types including (1) Euhedral to subhedral pyrite with internal fracturing and porous cores located in the sandstone layers (pyrite 1); (2) Anhedral pyrite overgrowths on pyrite 1 and disseminated in stage 1 vein (pyrite 2); (3) Fracture-filled or vein pyrite located in stages 1 and 2 vein (pyrite 3); (4) Euhedral pyrite with internal fractures also located in stage 2 vein (pyrite 4); and (5) Subhedral clean pyrite located in the rhyolite intrusion (pyrite 5). Based on pyrite mapping and spot analyses, two main stages of gold enrichment are documented from the Tersang gold deposit. Gold in sandstone-hosted pyrite 1 (mean 4.3 ppm) shows best correlation with Bi and Pb (as evidenced on pyrite maps). In addition, gold in pyrite 3 (mean 8 ppm) located in stage 2 vein shows a good correlation with As, Ag, Sb, Cu, Tl, and Pb. In terms of gold exploration, we suggest that elements such as As, Ag, Sb, Cu, Tl, Bi, and Pb associated with Au may serve as vectoring tools in gold exploration. Our new geological, structural, geochemical and isotopic data together with mineral paragenesis, pyrite chemistry and ore fluid characteristics indicate that the Tersang gold deposit is comparable to a sediment-hosted gold deposit. Our new genetic model suggests deposition of the Permo-Carboniferous sediments followed by intrusion of rhyolitic magma in the Late Triassic. At a later stage, gold mineralisation overprinted the rhyolite intrusion and the sandstone.

Application of protection means against explosions in underground mines

Underground coal mines explosions generally arise from the inflammation of a methane/air mixture. This explosion can also generate a subsequent coal dust explosion. Traditionally such explosions have being fought eliminating one or several of the factors needed by the explosion to take place. Although several preventive measures are taken to prevent explosions, other measures should be considered to reduce the effects or even to extinguish the flame front. Unlike other protection methods that remove one or two of the explosion triangle elements, namely; the ignition source, the oxidizing agent and the fuel, explosion barriers removes all of them: reduces the quantity of coal in suspension, cools the flame front and the steam generated by vaporization removes the oxygen present in the flame. The present paper is essentially based on the comprehensive state-of–the-art of Protective Systems in underground coal mines, and particularly on the application of Explosion Barriers to improve safety level in Spanish coal mining industry. After an exhaustive study of series EN 14591 standards covering explosion prevention and protection in underground mines, authors have proven explosion barriers effectiveness in underground galleries by Full Scale Tests performed in Polish Barbara experimental mine, showing that the barriers can reduce the effects of methane and/or flammable coal dust explosions to a satisfactory safety level.

La Planificación de Áreas Mineras en Declive : Una respuesta multidimensional = Planning Declining Mining Areas. A multidimensional response

La actividad minera tiene un gran impacto sobre el territorio, probablemente más que ninguna otra de las actividades humanas, ya que transforma el espacio en todas sus dimensiones: ecológica, ambiental, social y económica. Cuando la reducción de la rentabilidad de la explotación conduce al cierre de ésta, la repercusión sobre su entorno puede llegar a ser brutal. Pero las explotaciones mineras son muy distintas entre ellas y los efectos que su abandono producen sobre el espacio en la que se enclavan pueden ser diversos, por lo que la decisión sobre el futuro de estas áreas no es simple y evidente. Aquí se propone desarrollar una propuesta de clasificación tipológica de las minas y sus regiones con el objetivo de determinar las estrategias de intervención más adecuadas para el futuro de estos espacios y sus habitantes. En concreto se busca diferenciar los conceptos de Mina, Parque Minero, Espacio Minero y Región Minera, todos ellos fruto de la interacción de la huella de la actividad minera con el medio físico, los enclaves urbanizados, y la estructura socioeconómica de la región en la que se enclavan. Mining activity is having a great impact on the territory, probably more than any other human activity, which transforms the space in all of its dimensions, ecological, environmental, social and economic. When reducing the profitability of the operation leads to the conclusion thereof, the impact on the environment can be brutal. But mining are very different between them and the effects they produce on their abandonment in space that interlock can be diverse, so the decision on the future of these areas is not simple and obvious. This proposal aims to develop a typological classification of mines and their regions in order to determine the most appropriate intervention strategies for the future of these spaces and their inhabitants. Specifically, it seeks to differentiate the concepts of Mine, Mining Park, Space Miner and Mining Region, all the result of the interaction of the mining footprint with the physical environment, the urbanized enclaves, and the socio-economic structure of the region which interlock. El presente libro reúne las ponencias presentadas por los investigadores de la red REUSE dentro del 1er Simposio de Reutilización del Espacio Minero; evento organizado por la Universidad Federal de Minas Gerais (UFMG) en Belo Horizonte, entre el 1 y el 3 de octubre de 2012, en el marco del 1er Seminario Internacional de Reconversión de Territorios. La red REUSE es una red realizada gracias a la financiación del programa CYTED

Las mineralizaciones auríferas de Galicia Occidental en la Zona de Cizalla Busto-Limideiro (A Coruña)

Las mineralizaciones de oro de Galicia Occidental ligadas a grandes estructuras comienzan a ser interpretadas de manera más rigurosa, al mismo tiempo que la continuada elevación de las cotizaciones del oro han hecho más atractiva la reactivación de áreas hasta ahora casi olvidadas. El propósito de esta investigación participa de las razones anteriores. La zona de cizalla Busto Limideiro se inscribe en una de estas estructuras, la cizalla Santa Comba-Punta Langosteira, con la que se relacionan un importante número de yacimientos auríferos entre los que destacan Corcoesto y Monte Piñor. Por su situación geológica, estos indicios se enmarcan en el Macizo Ibérico, en la Zona de Galicia Tras-os-Montes. Este trabajo aporta más conocimiento sobre un modelo general del oro de los yacimientos del noroeste español, integrándolo en los yacimientos de oro orogénico del Varisco europeo. Este estudio ha supuesto un importante esfuerzo investigador centrado sobre de los procesos genéticos que han dado lugar a las mineralizaciones auríferas. Los estudios petrográficos, metalogénicos, geoquímicos, microtemométricos y el análisis de isótopos han permitido establecer un modelo general y otros más específicos sobre la existencia y condiciones de formación en la concentración del oro mineralógico. De esta forma se ha caracterizado su mineralogía, quimismo, edad, y naturaleza de los paleofluidos que han intervinieron en su formación. De los resultados obtenidos se destaca que estas mineralizaciones se encuentran fuertemente ligadas a las estructuras y transformaciones físicas y químicas de las rocas afectadas por la banda de cizalla. Derivada de esta situación, se comprende la disposición espacial, a diversas escalas, con estructuras claramente en la transición del dominio dúctil a frágil. Además, resulta evidente, a escala macro y microscópica, el emplazamiento preferente del oro en estructuras de deformación miloníticas. Los estudios anteriores posibilitan formalizar un modelo de génesis para el yacimiento de Monte Piñor que resulta compatible con el establecido por Groves (1998), e incluirlas en un mismo contexto, como yacimientos de oro orogénico mesotermales, válido para el conjunto de todos los de la zona de cizalla Busto Limideiro. El estudio no omite la consideración geoestadística de este yacimiento, justificando la elección de direcciones de anisotropía explicadas por consideraciones de carácter estructural. Con ello, buscando el lado práctico desde el punto de vista minero, esta investigación propone líneas generales de aplicación de actuación con sentido de exploración, contribuyendo a la puesta en valor del conocimiento de las mineralizaciones de oro del noroeste español. ABSTRACT Old and nearly forgotten gold mines from Western Galicia are currently attractive to be recovered due to both, the new strict interpretation of gold mineralization linked to Variscan large structures and the increasing gold prices. The shear zone Busto Limiderio is relevant as a part of a Variscan large structure, Santa Comba-Punta Langosteira, which is related with a high number of gold deposits as Corcoesto and Monte Piñor. For its geological situation, these signs are part of the Iberian Massif in the area of Galicia Tras-os-Montes. Hence, the main aim of this study is to provide additional and important knowledge of Busto Limiderio about the general model of gold deposits in the Spanish northwest, integrating them in the orogenic gold deposits of European Variscan, enabling to analyze the economic recovery possibility of this area. This thesis has been focused on the genetic processes that have led to the gold mineralization. Petrographic studies, metalogenic, geochemical, microthermometric and isotope analysis have allowed to establish a general and specific models about the existence and training conditions in the concentration of mineralogical gold. Consequently, the mineralogy, chemical characteristics, age, and nature of paleofluids that have participated in its formation have been characterized. The results showed that Busto Limiderio gold mineralization are strongly linked to the structures and physical and chemical transformations of affected rocks by the shear band. The mineralization spatial distribution at various scales is due to the link with the large structures in the ductile-to-brittle transition domain. Furthermore, this factor determine at macro and microscopic scale, the preferred location of the gold structures mylonitic deformation. Previous studies have permitted to establish a model of genesis for the site of Monte Piñor which is compatible with the established by Groves (1998), and also to include them in the same context as mesothermal orogenic gold deposits, valid throughout all of Busto Limideiro shear zone. This study does not omit consideration of the geostatistical deposit, justifying the choice of directions of anisotropy explained by structural considerations. This thesis concludes with general action guidelines for mining exploration, contributing to the enhancement of knowledge of Spanish gold mineralization northwest.

Inhibition of AP-1 binding and transcription by gold and selenium involving conserved cysteine residues in Jun and Fos.

Gold(I) salts and selenite, which have diverse therapeutic and biological effects, are noted for their reactivity with thiols. Since the binding of Jun-Jun and Jun-Fos dimers to the AP-1 DNA binding site is regulated in vitro by a redox process involving conserved cysteine residues, we hypothesized that some of the biological actions of gold and selenium are mediated via these residues. In electrophoretic mobility-shift analyses, AP-1 DNA binding was inhibited by gold(I) thiolates and selenite, with 50% inhibition occurring at approximately 5 microM and 1 microM, respectively. Thiomalic acid had no effect in the absence of gold(I), and other metal ions inhibited at higher concentrations, in a rank order correlating with their thiol binding affinities. Cysteine-to-serine mutants demonstrated that these effects of gold(I) and selenite require Cys272 and Cys154 in the DNA-binding domains of Jun and Fos, respectively. Gold(I) thiolates and selenite did not inhibit nonspecific protein binding to the AP-1 site and were at least an order of magnitude less potent as inhibitors of sequence-specific binding to the AP-2, TFIID, or NF1 sites compared with the AP-1 site. In addition, 10 microM gold(I) or 10 microM selenite inhibited expression of an AP-1-dependent reporter gene, but not an AP-2-dependent reporter gene. These data suggest a mechanism regulating transcription factor activity by inorganic ions which may contribute to the known antiarthritic action of gold and cancer chemoprevention by selenium.