Removal of sunscreen compounds from swimming pool water using self-organized TiO2 nanotubular array electrodes

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

Study of zinc hexacyanoferrate-modified platinum electrodes using electrochemical quartz crystal microbalance

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Botryoidal platinum, palladium and potarite from the Bom Sucesso stream, Minas Gerais, Brazil: Compositional zoning and origin

Platinum-Pd nuggets from the Born Sucesso stream alluvium Minas Gerais, Brazil. have been investigated by electron-probe microanalysis. The nuggets attain 1 mm in maximum dimension and have a botryoidal habit, with pronounced compositional core-to-margin zoning of internal structures, Although there is a wide variation in internal morphology and individual zones vary markedly in thickness (<1-100 mum), a typical composite arborescent nugget comprises a broad irregular core region of massive auriferous Pd-Hg alloy (potarite delta-PdHg) or cavity space + relict potarite enclosed by a narrow zone of platiniferous, palladium or alloy of near Pt50Pd50 composition, and is progressively oscillatory zoned by palladian platinum, with growth eventually enveloping the whole botryoidal colony, to a narrow rim of palladian platinum or pure platinum. Other nuggets comprise an arborescent to dendritic core of auriferous potarite, a broad internal zone of either pure platinum or palladian platinum, and a narrow rim of platinum, the mineral palladium contains up to about 65 at.% Pd; this is the first detailed modern confirmation of palladium in its type locality. Auriferous potarite ranges in composition from similar toPd(3)Hg(2) to near Pd(Hg,Au). The origin of these nuggets remains unclear, but their mineralogy is broadly equivalent to that of palladian gold. potarite and platinum in alluvial sediments and overburden from Devon, England, which are considered to be detrital, and their platinum-group-clement geochemistry is consistent with precipitation from hydrothermal fluids. We suggest that the Bom Sucesso nuggets resulted from high-level episodic hydrothermal alteration of mafic and ultramafic rocks within the drainage basin, with the remobilized Pt and Pd precipitated in open spaces in the enclosing metaquartzites.

Synthesis and characterization of a new platinum(II) complex with L-mimosine

Synthesis and characterization of a new Pt(II)-mimosine complex are described. Elemental, mass spectrometry and thermal analyses for the complex are consistent with the formula [PtCl2(C8H10N2O4)]center dot 1.5H(2)O. C-13 NMR, N-15 NMR and infrared spectroscopy indicate coordination of the ligand to Pt(II) through the N and O atoms in a square-planar geometry. The final residue after thermal treatment was identified as metallic Pt. The complex is soluble in dimethylsulfoxide.

Crystal structure and infrared analysis of a new trinuclear platinum(II) complex with L-cysteine

A new trinuclear platinum(II) complex with cysteine of composition [Pt(C3H6NO2S)Cl](3)center dot(C2H6SO)(3) was obtained and structurally characterized by X-ray diffraction and infrared analysis. The compound crystallizes in the trigonal system, space group R3, and is described in a hexagonal cell with a=17.739(1), c=9.531(1) and Z=3. Cysteine is coordinated to Pt(II) through the nitrogen and sulphur atoms. Each cysteine sulphur bridges between two metal atoms. A square planar coordination sphere of platinum is completed by a chlorine atom. The complex is soluble in dimethyl sulfoxide.

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

Platinum Group Minerals in Eastern Brazil GEOLOGY AND OCCURRENCES IN CHROMITITE AND PLACERS

Brazil does not have working platinum mines, nor even large reserves of the platinum metals, but there is platinum in Brazil. In this paper, four massifs (mafic/ultramafic complexes) in eastern Brazil, in the states of Minas Gerais and Ceara, where platinum is found will be described. Three of these massifs contain concentrations of platinum group minerals or platinum group elements, and gold, associated with the chromitite rock found there. In the fourth massif, in Minas Gerais State, the platinum group elements are found in alluvial deposits at the Bom Sucesso occurrence. This placer is currently being studied.

Amperometric differential determination of ascorbic acid in beverages and vitamin C tablets using a flow cell containing an array of gold microelectrodes modified with palladium

A simple and attractive method for quantification of ascorbic acid (AA) in beers, soda, natural juices and commercial vitamin C tablets was achieved by combining Bow injection analysis and amperometric detection. An array of gold microelectrodes electrochemically modified by deposition of palladium was employed as working electrode which was almost unaffected by fouling effects. Ascorbic acid was quantified in beverages and vitamin tablets using amperometric differential measurements. This method is based on three steps involving the flow injection of: 1) the sample plus a standard addition of AA, 2) the pure sample, and 3) the enzymatically-treated sample. The enzymatic treatment was carried out with Cucumis sativus tissue, which is a rich source of ascorbate oxidase, at pH 7. The calibration plots for freshly prepared ascorbic acid standards were very linear in the concentration range of 0.18-1.8 mg L-1 with a relative standard deviation (RSD) < 1%, while for real samples the deviations were between 2.7% to 8.9%.

The generator coordinate Hartree-Fock method as strategy for building Gaussian basis sets to ab initio study of the process of adsorption of sulfur on platinum (200) surface

The scheme named generator coordinate Hartree-Fock method (GCHF) is used to build (22s14p) and (33s22p16d9f) gaussian basis sets to S ((3)P) and Pt ((3)D) atoms, respectively. Theses basis sets are contracted to [13s10p] and [19s13p9d5f] through of Dunning's segmented contraction scheme and are enriched with d and g polarization functions, [13s10p1d] and [19s13p9d5flg]. Finally, the [19s13p9d5f1g] basis Set to Pt ((3)D) was supplemented with s and d diffuse functions, [20s13p10d5flg], and used in combination with [13s10p1d] to study the effects of adsorption of S ((3)D) atom on a pt ((3)D) atom belonged to infinite Pt (200) surface. Atom-atom overlap population, bond order, and infrared spectrum of [pt(_)S](2 -) were calculated properties and were carried out at Hartree-Fock-Roothaan level. The results indicate that the process of adsorption of S ((3)P) on pt ((3)D) in the infinite Pt (200) surface is mainly caused by a strong contribution of sigma between the 3p(z) orbital of S ((3)P) and the 6s orbital of pt ((3)D). (c) 2004 Elsevier B.V. All rights reserved.

Synthesis, characterization and initial biological studies of a new platinum(II) complex with deoxyalliin

A new platinum(II) complex with deoxyalliin was synthesized and characterized by chemical and spectroscopic techniques. Elemental and mass spectrometry analyses of the solid complex fit to the composition [Pt(C6H11NO2S)Cl-2] center dot H2O. C-13 NMR, N-15 NMR and infrared spectra of the complex are consistent with coordination of deoxyalliin to Pt( II) through the nitrogen and sulfur atoms forming a square-planar geometry. The complex is soluble in dimethylsulfoxide. Biological analysis for evaluation of a potential cytotoxic effect of the complex was performed using HeLa cells, a human cervix adenocarcinoma-derived cell line. The results were compared with those of a palladium( II) complex previously described.

Synthesis and X-ray structure of the dinuclear platinum(II) complex with saccharin {K[Pt(sac)(3)(H2O)] center dot H2O}(2): Studies on its antiproliferative activity in aqueous solution

Synthesis and X-ray structure of a dinuclear platinum(II) complex with the ligand saccharin(sac) are described. The structure shows two approximately square-planar platinum centers. Each platinum atom is coordinated to one water molecule and three N-bonded saccharinate ligands. The two centers are linked through two potassium atoms. Each potassium atom interacts with six oxygen atoms from hydration and coordinated water molecules and from carbonyl and sulfonate groups of the ligands. It is suggested that, in aqueous solution, the dimeric structure of the complex is dissociated and the monomeric species K[Pt(sac)(3)(H2O)] is formed. The complex was dissolved in water and submitted to in vitro cytotoxic analyses using HeLa cells (human cervix cancer). It was shown that the monomeric complex elicited a potent cytotoxic activity when compared to the vehicle-treated cells. The IC50 value for the monomeric complex is 6.8 mu M, a little bit higher than that obtained for cisplatin. (c) 2007 Elsevier B.V. All rights reserved.

Validation of an immunoassay method for the determination of traces of carbaryl in vegetable and fruit extracts by liquid chromatography with photodiode array and mass spectrometric detection

A competitive enzyme-linked immunosorbent assay (ELISA) method for carbaryl quantitation in crop extracts was validated by liquid chromatography (LC) with diode array detection (DAD). For this purpose, six crops (banana, carrot, green bean, orange, peach and potato) were chosen for recovery and reproducibility studies. The general sample preparation included extraction with methanol followed by liquid-liquid partitioning and clean-up on Celite-charcoal adsorbent column of the vegetable extracts. ELISA samples consisted of a diluted LC extract in assay phosphate buffer (pH 7.5). The potential effect of methanol in these samples was evaluated. It was observed that a maximum content of 10% methanol present in the assay buffer could be tolerated without expressive losses in the ELISA performance. Under these conditions, a IC50 similar to 1.48 mu g l(-1) was obtained. A minimum matrix effect with a 1:50 dilution of the methanolic extracts in assay buffer was noticed, except for green bean samples that inhibited completely the assay. For the vegetable extracts, the ELISA sensitivities varied from 3.9 to 5.7 mu g l(-1), and good recoveries (82-96%) with R.S.D.s ranging from 5.7 to 12.1% were found. An excellent correlation between the LC-DAD and ELISA techniques was obtained. The confirmation of the carbaryl in less concentrated samples was achieved by LC-mass spectrometry interfaced with atmospheric pressure chemical ionisation. The [M + H](+)= 202 and [M + H-57](+)=145 ions, equivalent to the protonated molecular and l-naphthol ions, respectively, were used to carbaryl identification in these samples. (C) 1998 Elsevier B.V. B.V. All rights reserved.

Thermogravimetry (TG) applied to the study of the reaction of mercury with platinum-rhodium alloy

Thermogravimetry (TG) energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface, X-ray diffraction (XRD), inductively coupled plasma emission spectroscopy and atomic spectroscopy with cold vapor generation have been used to study the reaction of mercury with platinum-rhodium (Pt-Rh) alloy. The results suggest that, the electrodeposited Hg film reacts with Pt-Rh to form intermetallic compounds of different stability, when heated indicated by at least four weight loss steps. Intermetallic compounds as PtHg4 and PtHg2 was characterized by XRD. These intermetallic compound are the main product presents on the surface of the samples after remotion of the bulk mercury via thermal desorption techniques. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Flow-through cell based on an array of gold microelectrodes obtained from modified integrated circuit chips

The construction of a flow-through cell incorporating an array of gold microelectrodes is described and its application to flow injection analysis with amperometric detection is presented, Simple modification of almost any conventional integrated circuit chip, used as an inexpensive source of pre-assembled gold micro-wires, leads to the rapid and successful preparation of arrays of 8-48 elements, the polymeric encapsulation material from the top face of the chip is removed by abrasion until the gold micro-mires (used to interconnect the silicon circuit to the external contact pins of the chip) are disrupted and their transversal (elliptical) sections become exposed. Once polished, the flat and smooth top surface of the gold microelectrode-array chip (MEAC) is provided with a spacer and fitted under pressure against an acrylic block with the reference and auxiliary electrodes, to form the electrochemical (thin-layer) flow cell, while the contact pins are plugged into a standard IC socket, This design ensures autonomous electric contact with each electrode and allows fast dismantling for polishing or substitution, the performance of flow cells with MEACs was investigated utilizing the technique of reverse pulse amperometry without oxygen removal, A method was established for the determination of the copper concentration in sugar cane spirit, regulated by law for beverages, Samples from industrial producers and small-scale (alembic) brewers were compared, With a 24 MEAC, a detection limit of 30 mu g I-l of copper (4.7 x 10(-7) mol l(-1) of Cu-II for 100 mu l injections) was calculated, Routine operation was established at a frequency of 60-90 determinations per hour, Intercomparison with atomic absorption spectrometric determinations resulted in excellent agreement.