Supramolecular Gold Metallogelators: The Key Role of Metallophilic Interactions

Gold metallogelators is an emerging area of research. The number of results published in the literature is still scarce. The majority of these gels is observed in organic solvents, and the potential applications are still to be explored. In this work, we present an overview about gold metallogelators divided in two different groups depending on the type of solvent used in the gelation process (organogelators and hydrogelators). A careful analysis of the data shows that aurophilic interactions are a common motif directly involved in gelation involving Au(I) complexes. There are also some Au(III) derivatives able to produce gels but in this case the organic ligands determine the aggregation process. A last section is included about the potential applications that have been reported until now with this new and amazing class of supramolecular assemblies.

Modeling of Gold Cyanidation

The chemistry of gold dissolution in alkaline cyanide solution has continually received attention and new rate equations expressing the gold leaching are still developed. The effect of leaching parameters on gold gold cyanidation is studied in this work in order to optimize the leaching process. A gold leaching model, based on the well-known shrinking-core model, is presented in this work. It is proposed that the reaction takes place at the reacting particle surface which is continuously reduced as the reaction proceeds. The model parameters are estimated by comparing experimental data and simulations. The experimental data used in this work was obtained from Ling et al. (1996) and de Andrade Lima and Hodouin (2005). Two different rate equations, where the unreacted amount of gold is considered in one equation, are investigated. In this work, it is presented that the reaction at the surface is the rate controlling step since there is no internal diffusion limitation. The model considering the effect of non-reacting gold shows that the reaction orders are consistent with the experimental observations reported by Ling et al. (1996) and de Andrade Lima and Hodouin (2005). However, it should be noted that the model obtained in this work is based on assumptions of no side reactions, no solid-liquid mass transfer resistances and no effect from temperature.

Surface Studies of Thiolate Adsorbates on Some Metals

The results and discussions in this thesis are based on my studies about selfassembled thiol layers on gold, platinum, silver and copper surfaces. These kinds of layers are two-dimensional, one molecule thick and covalently organized at the surface. They are an easy way to modify surface properties. Self-assembly is today an intensive research field because of the promise it holds for producing new technology at nanoscale, the scale of atoms and molecules. These kinds of films have applications for example, in the fields of physics, biology, engineering, chemistry and computer science. Compared to the extensive literature concerning self-assembled monolayers (SAMs) on gold, little is known about the structure and properties of thiolbased SAMs on other metals. In this thesis I have focused on thiol layers on gold, platinum, silver and copper substrates. These studies can be regarded as a basic study of SAMs. Nevertheless, an understanding of the physical and chemical nature of SAMs allows the correlation between atomic structure and macroscopic properties. The results can be used as a starting point for many practical applications. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation excited high resolution photoelectron spectroscopy (HR-XPS) together with time-offlight secondary ion mass spectrometry (ToF-SIMS) were applied to investigate thin organic films formed by the spontaneous adsorption of molecules on metal surfaces. Photoelectron spectroscopy was the main method used in these studies. In photoelectron spectroscopy, the sample is irradiated with photons and emitted photoelectrons are energy-analyzed. The obtained spectra give information about the atomic composition of the surface and about the chemical state of the detected elements. It is widely used in the study of thin layers and is a very powerful tool for this purpose. Some XPS results were complemented with ToF-SIMS measurements. It provides information on the chemical composition and molecular structure of the samples. Thiol (1-Dodecanethiol, CH3(CH2)11SH) solution was used to create SAMs on metal substrates. Uniform layers were formed on most of the studied metal surfaces. On platinum, surface aligned molecules were also detected in investigations by XPS and ToF-SIMS. The influence of radiation on the layer structure was studied, leading to the conclusion that parts of the hydrocarbon chains break off due to radiation and the rest of the layer is deformed. The results obtained showed differences depending on the substrate material. The influence of oxygen on layer formation was also studied. Thiol molecules were found to replace some of the oxygen from the metal surfaces.

Spectroscopic characterization of phases formed by high-dose carbon ion implantation in silicon

High-dose carbon-ion-implanted Si samples have been analyzed by infrared spectroscopy, Raman scattering, and x-ray photoelectron spectroscopy (XPS) correlated with transmission electron microscopy. Samples were implanted at room temperature and 500°C with doses between 1017 and 1018 C+/cm2. Some of the samples were implanted at room temperature with the surface covered by a capping oxide layer. Implanting at room temperature leads to the formation of a surface carbon-rich amorphous layer, in addition to the buried implanted layer. The dependence of this layer on the capping oxide suggests this layer to be determined by carbon migration toward the surface, rather than surface contamination. Implanting at 500°C, no carbon-rich surface layer is observed and the SiC buried layer is formed by crystalline ßSiC precipitates aligned with the Si matrix. The concentration of SiC in this region as measured by XPS is higher than for the room-temperature implantation.

Ion-selective electrodes: historical, mechanism of response, selectivity and concept review

This paper presents a review of the concepts involved in the working mechanism of the ion-selective electrodes, searching a historical overview, moreover to describe the new advances in the area.

Gas-phase ion chemistry of silyl cations obtained from hexamethyldisilazane

The gas-phase ion-molecule reactions of the Me3SiN(H)SiMe2+ ion, obtained by electron ionization from Me3SiN(H)SiMe3, have been studied in a Fourier transform ion cyclotron resonance spectrometer in order to understand the mechanistic details of an important chemical system presently used in film formation. This silyl cation has been observed to undergo addition reactions at electron rich centers to form stable adducts that may undergo further methane elimination in the case of alcohols and amines. The most important feature of these reactions is the fact that a metathesis type reaction can be observed in the presence of H2O, and other hydrogen labile substrates like alcohols, leading to the formation of the corresponding oxygen-containing ion, i.e. Me3SiOSiMe2+. For alcohols (ROH), facile formation of a tertiary product ion, presumably corresponding to an Me3Si-O-Si(Me)=O+-R structure with elimination of an amine reveals the strong tendency of these nitrogen-containing ions to undergo metathesis type reactions with oxygen containing substrates.

Síntese eletroquímica do ion ferrato(VI)

The optimization of ferrate(VI) ion generation has been studied due to its favorable characteristics for application in several fields, including environmental quality control. The paper presents the best conditions for electrolytic generation of ferrate(VI) in alkaline media. An appropriate electrolyte was NaOH, 10 mol/L. Circulation of the electrolyte solution was important to avoid acidification close to the anode surface. An anode pre-cleaning with 10% HCl was more efficient than a cathodic pre-polarization. Among the distinct anode materials tested, pig iron showed the best performance, allowing up to 20 g/L of Na2FeO4, in 10 mol/L NaOH solution to be obtained, after 7 h of reactor operation, which is a concentration higher than those found in literature for alternative processes.

Development and validation of an alternative titration method for the determination of sulfate ion in indinavir sulfate

A simple and rapid precipitation titration method was developed and validated to determine sulfate ion content in indinavir sulfate raw material. 0.1 mol L-1 lead nitrate volumetric solution was used as titrant employing potentiometric endpoint determination using a lead-specific electrode. The United States Pharmacopoeia Forum indicates a potentiometric method for sulfate ion quantitation using 0.1 mol L-1 lead perchlorate as titrant. Both methods were validated concerning linearity, precision and accuracy, yielding good results. The sulfate ion content found by the two validated methods was compared by the statistical t-student test, indicating that there was no statistically significant difference between the methods.

Obtenção de filmes espessos de seleneto de cobre sobre carbono vítreo, ouro, titânio e cobre

Copper selenide (berzelianite) films were prepared on the title substrates using the chemical bath deposition technique (CBD). Film composition was determined by energy dispersion of x-rays. The kinetics of film growth is parabolic and film adherence limits the film thickness. On titanium, copper selenide forms islands that do not completely cover the surface, unless the substrate is prepared with a tin oxide layer; film composition also depends on the titanium oxide layer. On vitreous carbon, CBD and mechanical immobilization techniques lead to films with similar resistances for the electron transfer across the film/substrate interface. On gold, composition studies revealed that film composition is always the same if the pH is in the range from 8 to 12, in contrast to films prepared by an ion-ion combination route. On copper, a new procedure for obtaining copper selenide films as thick as 5 µm has been developed.

Mercury in soils and sediments from gold mining liabilities in Southern Amazonia

The 1980-1990 Amazonian gold rush left an enormous liability that increasingly has been substituted by developing fish aquaculture. This work aimed at the identification of the mercury levels in the environment, associated with fish farms located in the North of Mato Grosso State, Southern Amazon. Sediment and soil samples were analyzed for total organic carbon and total mercury. Results indicate that the chemical characteristics of the sediment largely depend on the management procedures of the fish pond (liming, fish food used and fish population). The soils presented relatively low concentrations when compared with other data from the literature.

Optical and microstructural properties of MgF2 UV coatings grown by ion beam sputtering process

The optical, mechanical, and microstructural properties of MgF2 single layers grown by ion beam sputtering have been investigated by spectrophotometric measurements, film stress characterization, x-ray photoelectron spectroscopy (XPS), x-ray diffraction, and transmission electron microscopy. The deposition conditions, using fluorine reactive gas or not, have been found to greatly influence the optical absorption and the stress of the films as well as their microstructure. The layers grown with fluorine compensation exhibit a regular columnar microstructure and an UV-optical absorption which can be very low, either as deposited or after thermal annealings at very low temperatures. On the contrary, layers grown without fluorine compensation exhibit a less regular microstructure and a high ultraviolet absorption which is particularly hard to cure. On the basis of calculations, it is shown that F centers are responsible for this absorption, whereas all the films were found to be stoichiometric, in the limit of the XPS sensitivity. On the basis of external data taken from literature, our experimental curves are analyzed, so we propose possible diffusion mechanisms which could explain the behaviors of the coatings.

Arsenic mobilization from sulfidic materials from gold mines in Minas Gerais State

Acid drainage results from exposition of sulfides to the atmosphere. Arsenopyrite is a sulfide that releases arsenic (As) to the environment when oxidized. This work evaluated the As mobility in six sulfidic geomaterials from gold mining areas in Minas Gerais State, Brazil. Grained samples (<2 mm) were periodically leached with distilled water, during 70 days. Results suggested As sorption onto (hydr)oxides formed by oxidation of arsenopyrite. Low pH accelerated the acid generation, dissolving Fe oxihydroxides and releasing As. Presence of carbonates decreased oxidation rates and As release. On the other hand, lime added to a partially oxidized sample increased As mobilization.

Highly selective transport of mercury(II) ion through a bulk liquid membrane

In this work carrier-facilitated transport of mercury(II) against its concentration gradient from aqueous 0.04 M hydrochloric acid solution across a liquid membrane containing isopropyl 2-[(isopropoxycarbothiolyl)disulfanyl]ethane thioate (IIDE) as the mobile carrier in chloroform has been investigated. Sodium thiocyanate solution (1.6 M) was the most efficient receiving phase agent among several aqueous reagents tested. Various parameters such as investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is more than 97% after 2.5 h. The carrier, IIDE, selectively and efficiently could able to transport Hg (II) ions in the presence of other associated metal ions in binary systems.

Determination of nitrate in lettuce by ion chromatography after microwave water extraction

Lettuce is worldwide known as the most important vegetable. In this context, most farmers are searching new techniques for best quality products including hydropony. However, nitrate is of great concern, since it has a negative impact on human metabolism. The main objective of the present work was to evaluate the nitrate content of lettuce produced by conventional and hydroponic systems. The determination was conducted by ion chromatography and a new method of extraction was tested using microwave oven digestion. The results indicated that nitrate level produced in the conventional system was lower than in the hydroponic system.