Theoretical Approach for the Luminescent Properties of Ir(III) Complexes to Produce Red-Green-Blue LEC Devices.

With an appropriate mixture of cyclometalating and ancillary ligands, based on simple structures (commercial or easily synthesized), it has been possible to design a family of eight new Ir(III) complexes (1A, 1B, 2B, 2C, 3B, 3C, 3D and 3E) useful as luminescent materials in LEC devices. These complexes involved the use of phenylpyridines or fluorophenylpyridines as cyclometalating ligands and bipyridine or phenanthroline-type structures as ancillary ligands. The emitting properties have been evaluated from a theoretical approach through Density Functional Theory and Time-Dependent Density Functional Theory calculations, determining geometric parameters, frontier orbital energies, absorption and emission energies, injection and transport parameters of holes and electrons, and parameters associated with the radiative and non-radiative decays. With these complexes it was possible to obtain a wide range of emission colours, from deep red to blue (701-440 nm). Considering all the calculated parameters between all the complexes, it was identified that 1B was the best red, 2B was the best green, and 3D was the best blue emitter. Thus, with the mixture of these complexes, a dual host-guest system with 3D-1B and an RGB (red-green-blue) system with 3D-2B-1B are proposed, to produce white LECs.

Red-emitting heteroleptic iridium(III) complexes: photophysical and cell labeling study.

Two red-emitting heteroleptic iridium(III) complexes (Ir-p and Ir-q) were synthesized and their photophysical and biological properties were analyzed. After their structures have been confirmed by several techniques, such as 1H NMR, 13C NMR, FT-IR, UV-Vis, and MALDI TOF analyses, their luminescence behavior was investigated in ethanol and PBS (physiological medium, pH ~ 7.4) solutions. Emission spectra of both complexes are dominated by 3MLCT states at room temperature in ethanolic solution, but at 77 K the Ir-q exhibits the 3LC as the dominant emission state. The Ir-q complex shows one of the highest emission quantum yields, 11.5%, for a red emitter based on iridium(III) complexes in aerated PBS solution, with color coordinates (x;y) of (0.712;0.286). Moreover, both complexes display high potential to be used as a biological marker with excitation wavelengths above 400 nm, high water solubility (Ir-p 1838 µmol L-1, Ir-q 7601 µmol L-1), and distinct emission wavelengths from the biological autofluorescence. Their cytotoxicity was analyzed in CHO-k1 cells by MTT assays, and the IC50 was estimated as being higher than 131 µmol L-1 for Ir-p, and higher than 116 µmol L-1 for Ir-q. Concentrations above 70% of viability were used to perform cell imaging by confocal and fluorescence microscopies and the results suggest that the complexes were internalized by the cell membrane and they are staining the cytoplasm region.

Total Synthesis and Structural Validation of Phosdiecin A via Asymmetric Alcohol-Mediated Carbonyl Reductive Coupling.

The first total synthesis and structural validation of phosdiecin A was accomplished in 13 steps through asymmetric iridium-catalyzed alcohol-mediated carbonyl reductive coupling. The present route is the shortest among >30 total and formal syntheses of fostriecin family members.

Efficient cephalexin degradation using active chlorine produced on ruthenium and iridium oxide anodes: Role of bath composition, analysis of degradation pathways and degradation extent.

The elimination of cephalexin (CPX) using electro-generated Cl2-active on Ti/RuO2-IrO2 anode was assessed in different effluents: deionized water (DW), municipal wastewater (MWW) and urine. Single Ti/RuO2 and Ti/IrO2 catalysts were prepared to compare their morphologies and electrochemical behavior against the binary DSA. XRD and profile refinement suggest that Ti/RuO2-IrO2 forms a solid solution, where RuO2 and IrO2 growths are oriented by the TiO2 substrate through substitution of Ir by Ru atoms within its rutile-type structure. SEM reveals mud-cracked structures with flat areas for all catalysts, while EDS analysis indicates atomic ratios in the range of the oxide stoichiometries in the nominal concentrations used during synthesis. A considerably higher CPX degradation is achieved in the presence of NaCl than in Na2SO4 or Na3PO4 media due to the active chlorine generation. A faster CPX degradation is reached when the current density is increased or the pH value is lowered. This last behavior may be ascribed to an acid-catalyzed reaction between HClO and CPX. Degradation rates of 22.5, 3.96, and 0.576 µmol L-1 min-1 were observed for DW, MWW and urine, respectively. The lower efficiency measured in these last two effluents was related to the presence of organic matter and urea in the matrix. A degradation pathway is proposed based on HPLC-DAD and HPLC-MS analysis, indicating the fast formation (5 min) of CPX-(S)-sulfoxide and CPX-(R)-sulfoxide, generated due the Cl2-active attack at the CPX thioether. Furthermore, antimicrobial activity elimination of the treated solution is reached once CPX, and the initial by-products are considerably eliminated. Finally, even if only 16% of initial TOC is removed, BOD5 tests prove the ability of electro-generated Cl2-active to transform the antibiotic into biodegradable compounds. A similar strategy can be used for the abatement of other recalcitrant compounds contained in real water matrices such as urine and municipal wastewaters.

Reaching Biocompatibility with Nanoclays: Eliminating the Cytotoxicity of Ir(III) Complexes.

Cyclometalated IrIII complexes are promising candidates for biomedical applications but high cytotoxicity limits their use as imaging and sensing agents. We herein introduce the use of Laponite as carrier for triplet-emitting cyclometalated IrIII complexes. Laponite is a versatile nanoplatform because of its biocompatibility, dispersion stability and large surface area that readily adsorbs functional nonpolar and cationic molecules. These inorganic-organic hybrid nanomaterials mask cytotoxicity, show efficient cell uptake and increase luminescent properties and photostability. By camouflaging intrinsic cytotoxicity, this simple method potentially extends the palette of available imaging and sensing dyes to any metal-organic complexes, especially those that are usually cytotoxic.

"Click" Methodology for the Functionalization of Water Oxidation Catalyst Iridium Oxide Nanoparticles with Hydrophobic Dyes for Artificial Photosynthetic Constructs.

The unusually high tolerance toward chemical functional groups of the copper(I)-catalyzed Huisgen-Sharpless-Meldal 1,3-dipolar cycloaddition of azides and alkynes protocol (the CuAAC or "click" reaction) associated with its mild conditions and high yields has been explored in the present methodology to successfully prepare water oxidation catalyst iridium oxide nanoparticles decorated with organic dyes. The "click reaction" has proven to be an excellent synthetic tool to overcome the incompatible solubility of the hydrophilic iridium oxide nanoparticles and the hydrophobic dyes. A complex artificial photosynthetic model designed to mimic the photoinduced redox processes occurring in photosystem II is used as a hydrophobic dye to highlight the efficiency and selectiveness of the method.

Does Plan B work? Home range estimations from stored on board and transmitted data sets produced by GPS-telemetry in the Colombian Amazon / ¿Funciona el plan B? Estimación de rango de hogar a partir de datos almacenados en instrumentos a bordo de animales y los obtenidos a partir de telemetría satelital de GPS en el Amazonas colombiano

Abstract:Telemetry based on Global Positioning Systems (GPS) makes possible to gather large quantities of information in a very fine scale and work with species that were impossible to study in the past. When working with GPS telemetry, the option of storing data on board could be more desirable than the sole satellite transmitted data, due to the increase in the amount of locations available for analysis. Nonetheless, the uncertainty in the retrieving of the collar unit makes satellite-transmitted technologies something to take into account. Therefore, differences between store-on-board (SoB) and satellite-transmitted (IT) data sets need to be considered. Differences between SoB and IT data collected from two lowland tapirs (Tapirus terrestris), were explored by means of the calculation of home range areas by three different methods: the Minimum Convex Polygon (MCP), the Fixed Kernel Density Estimator (KDE) and the Brownian Bridges (BB). Results showed that SoB and IT data sets for the same individual were similar, with fix ranging from 63 % to 85 % respectively, and 16 m to 17 m horizontal errors. Depending on the total number of locations available for each individual, the home ranges estimated showed differences between 2.7 % and 79.3 %, for the 50 % probability contour and between 9.9 % and 61.8 % for the 95 % probability contour. These differences imply variations in the spatial coincidence of the estimated home ranges. We concluded that the use of IT data is not a good option for the estimation of home range areas if the collar settings have not been designed specifically for this use. Nonetheless, geographical representations of the IT based estimators could be of great help to identify areas of use, besides its assistance to locate the collar for its retrieval at the end of the field season and as a proximate backup when collars disappear. Rev. Biol. Trop. 64 (4): 1441-1450. Epub 2016 December 01.

Resumen:La telemetría basada en los sistemas de geopocisionamiento global (GPS) hace posible recopilar gran cantidad de información a escalas muy finas, y trabajar con especies imposibles de estudiar en el pasado. Al trabajar con telemetría de GPS, la opción de guardar información en la memoria interna del instrumento puede ser más deseable que sólo tener acceso a la información enviada vía satélite, debido a la mayor cantidad de localizaciones disponibles para analizar. No obstante, la incertidumbre de recuperar el collar hace que las tecnología de trasmisión vía satélite deba ser tenida en cuenta. Diferencias entre las bases de datos almacenadas en el collar (SoB) y las trasmitidas vía satélite (IT), recolectadas de dos individuos de Tapir de tierras bajas (Tapirus terrestris), son consideradas, en términos de las áreas de los rangos de hogar calculados con cada uno y mediante el uso de tres metodologías diferentes: Mínimo Polígono Convexo (MCP), Estimador de Densidad de Kernel Fijo (KDE) y los Puentes Brownianos (BB). Las bases de datos SoB e IT son similares, con tasas de acierto de localizaciones que oscilan entre 63 % to 85 % y errores horizontales de 16 m y 17 m respectivamente. Dependiendo del número total de localizaciones disponibles para cada individuo, los rangos de hogar estimados muestran diferencias entre 2.7 % y 79.3 %, para el contorno del 50 % de probabilidades, y entre 9.9 % y 61.8 % para el contorno del 95 % de probabilidades. Estas diferencias implican variaciones en la coincidencia espacial de los rangos de hogar estimados. Concluimos que el uso de la información trasmitida vía satélite no es una buena opción para la estimación de rangos de hogar, si la programción de los collares no ha sido diseñada específicamente para tal fin. Sin embargo, las representaciones geográficas de los estimados a partir de las bases de datos IT pueden ser de gran ayuda para la identificación de áreas de uso, además de su utilidad para la localización y recuperación de collares tras su liberación de los individuos monitoreados y como una base de datos de soporte en caso de pérdida del collar.

Does Plan B work? Home range estimations from stored on board and transmitted data sets produced by GPS-telemetry in the Colombian Amazon.

Telemetry based on Global Positioning Systems (GPS) makes possible to gather large quantities of information in a very fine scale and work with species that were impossible to study in the past. When working with GPS telemetry, the option of storing data on board could be more desirable than the sole satellite transmitted data, due to the increase in the amount of locations available for analysis. Nonetheless, the uncertainty in the retrieving of the collar unit makes satellite-transmitted technologies something to take into account. Therefore, differences between store-on-board (SoB) and satellite-transmitted (IT) data sets need to be considered. Differences between SoB and IT data collected from two lowland tapirs (Tapirus terrestris), were explored by means of the calculation of home range areas by three different methods: the Minimum Convex Polygon (MCP), the Fixed Kernel Density Estimator (KDE) and the Brownian Bridges (BB). Results showed that SoB and IT data sets for the same individual were similar, with fix ranging from 63 % to 85 % respectively, and 16 m to 17 m horizontal errors. Depending on the total number of locations available for each individual, the home ranges estimated showed differences between 2.7 % and 79.3 %, for the 50 % probability contour and between 9.9 % and 61.8 % for the 95 % probability contour. These differences imply variations in the spatial coincidence of the estimated home ranges. We concluded that the use of IT data is not a good option for the estimation of home range areas if the collar settings have not been designed specifically for this use. Nonetheless, geographical representations of the IT based estimators could be of great help to identify areas of use, besides its assistance to locate the collar for its retrieval at the end of the field season and as a proximate backup when collars disappear.

Photocatalytic fluoroalkylation reactions of organic compounds.

Photocatalytic methods for fluoroalkyl-radical generation provide more convenient alternatives to the classical perfluoroalkyl-radical (Rf) production through chemical initiators, such as azo or peroxide compounds or the employment of transition metals through a thermal electron transfer (ET) initiation process. The mild photocatalytic reaction conditions tolerate a variety of functional groups and, thus, are handy to the late-stage modification of bioactive molecules. Transition metal-photocatalytic reactions for Rf radical generation profit from the redox properties of coordinatively saturated Ru or Ir organocomplexes to act as both electron donor and reductive species, thus allowing for the utilization of electron accepting and donating fluoroalkylating agents for Rf radical production. On the other hand, laboratory-available and inexpensive photoorgano catalysts (POC), in the absence of transition metals, can also act as electron exchange species upon excitation, resulting in ET reactions that produce Rf radicals. In this work, a critical account of transition metal and transition metal-free Rf radical production will be described with photoorgano catalysts, studying classical examples and the most recent investigations in the field.

Antimicrobial and cytotoxic effects of phosphoric acid solution compared to other root canal irrigants

Phosphoric acid has been suggested as an irrigant due to its effectiveness in removing the smear layer. Objectives : The purpose of this study was to compare the antimicrobial and cytotoxic effects of a 37% phosphoric acid solution to other irrigants commonly used in endodontics. Material and Methods : The substances 37% phosphoric acid, 17% EDTA, 10% citric acid, 2% chlorhexidine (solution and gel), and 5.25% NaOCl were evaluated. The antimicrobial activity was tested against Candida albicans, Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Actinomyces meyeri, Parvimonas micra, Porphyromonas gingivalis, and Prevotella nigrescens according to the agar diffusion method. The cytotoxicity of the irrigants was determined by using the MTT assay. Results : Phosphoric acid presented higher antimicrobial activity compared to the other tested irrigants. With regard to the cell viability, this solution showed results similar to those with 5.25% NaOCl and 2% chlorhexidine (gel and solution), whereas 17% EDTA and 10% citric acid showed higher cell viability compared to other irrigants. Conclusion : Phosphoric acid demonstrated higher antimicrobial activity and cytotoxicity similar to that of 5.25% NaOCl and 2% chlorhexidine (gel and solution). .

Direct Method for Determination of Al, Cd, Cu, and Pb in Beers In Situ Digested by GF AAS Using Permanent Modifiers.

The object of the present study was to development of safe, reliable fast, and efficient methodologies for the direct determination of Al, Pb, Cu, and Cd in non-digested beer samples of widely consumed brand name beers sold in Brazil, using graphite furnace absorption spectrometry (GF AAS). Pyrolysis and atomization temperature curves of selected chemical modifiers (iridium, rhodium, ruthenium, zirconium, and non-modifier use) were used to stabilize each metal and sensitivity in a beer sample was diluted to 1:1 with 0.2 % v/v nitric acid after degasification. The best modifier for aluminum was permanent zirconium, with a characteristic mass of 4.2 pg (recommended is 10 pg), demonstrating a symmetrical peak with a corrected background using a deuterium arc lamp. For cadmium and copper, the best modifier was permanent ruthenium with characteristic masses of 0.3 and 7 pg (recommended are 0.35 and 4 pg, respectively, for Cd and Cu), respectively. The best condition for lead was using a non-modifier, with a characteristic mass of 6.9 pg (recommended is 10 pg). The limits of detection and mean recoveries, done over three consecutive days for aluminum, copper, lead, and cadmium, were 1.9, 2.9, 0.8, and 0.6 pg and 105, 104, 101, and 102 %, respectively. From the observed results, we may conclude that some metals, such as Al, Cd, Cu, and Pb, can be determined easily with graphite furnace atomic absorption spectrometry without sample digestion using a dilute nitric acid solution.

Interaction between proteins and Ir based CO releasing molecules: mechanism of adduct formation and CO release.

Carbon monoxide releasing molecules (CORMs) have important bactericidal, anti-inflammatory, neuroprotective, and antiapoptotic effects and can be used as tools for CO physiology experiments, including studies on vasodilation. In this context, a new class of CO releasing molecules, based on pentachlorocarbonyliridate(III) derivative have been recently reported. Although there is a growing interest in the characterization of protein-CORMs interactions, only limited structural information on CORM binding to protein and CO release has been available to date. Here, we report six different crystal structures describing events ranging from CORM entrance into the protein crystal up to the CO release and a biophysical characterization by isothermal titration calorimetry, Raman microspectroscopy, and molecular dynamics simulations of the complex between a pentachlorocarbonyliridate(III) derivative and hen egg white lysozyme, a model protein. Altogether, the data indicate the formation of a complex in which the ligand can bind to different sites of the protein surface and provide clues on the mechanism of adduct formation and CO release.

Relationship between anode material, supporting electrolyte and current density during electrochemical degradation of organic compounds in water.

Taking crystal violet (CV) dye as pollutant model, the electrode, electrolyte and current density (i) relationship for electro-degrading organic molecules is discussed. Boron-doped diamond (BDD) or Iridium dioxide (IrO2) used as anode materials were tested with Na2SO4 or NaCl as electrolytes. CV degradation and generated oxidants showed that degradation pathways and efficiency are strongly linked to the current density-electrode-electrolyte interaction. With BDD, the degradation pathway depends on i: If ii(lim), generated oxidants play a major role in the CV elimination. When IrO2 was used, CV removal was not dependent on i, but on the electrolyte. Pollutant degradation in Na2SO4 on IrO2 seems to occur via IrO3; however, in the presence of NaCl, degradation was dependent on the chlorinated oxidative species generated. In terms of efficiency, the Na2SO4 electrolyte showed better results than NaCl when BDD anodes were employed. On the contrary, NaCl was superior when combined with IrO2. Thus, the IrO2/Cl(-) and BDD/SO4(2-) systems were better at removing the pollutant, being the former the most effective. On the other hand, pollutant degradation with the BDD/SO4(2-) and IrO2/Cl(-) systems is favored at low and high current densities, respectively.

Development of biosensor for phenolic compounds containing PPO in ß-cyclodextrin modified support and iridium nanoparticles.

A biosensor based on the iridium nanoparticles dispersed in ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate (Ir-BMI·PF6) and a celery (Apium graveolens) extract as a source of polyphenol oxidase (PPO) was constructed. A modified support based on ß-cyclodextrin (ß-CDEP) was used for enzyme immobilization. The behavior of phenolic compounds was investigated by square-wave voltammetry and rutin was selected by presenting the greatest signal. The best performance was obtained with a composition of 70:10:10:10% (w/w/w/w) of the graphite powder:ß-CDEP:Nujol:Ir-BMI·PF6 composition, a PPO concentration of 500unitsmL(-1), in 0.1M phosphate buffer solution (pH 6.0) with frequency, pulse amplitude and scan increment at 100Hz, 60mV, and 3.0mV, respectively. Under optimized conditions, the cathodic currents increased linearly for the rutin concentration range of 1.3×10(-7)-2.0×10(-6)M with a detection limit of 7.9×10(-8)M. This sensor demonstrated acceptable repeatability and reproducibility and the results for the rutin recovery ranged from 92.8 to 103.4%. A relative error of 0.7% was obtained in the rutin determination in simulated samples.

Accumulation of impact markers in desert wetlands and implications for the Younger Dryas impact hypothesis.

The Younger Dryas impact hypothesis contends that an extraterrestrial object exploded over North America at 12.9 ka, initiating the Younger Dryas cold event, the extinction of many North American megafauna, and the demise of the Clovis archeological culture. Although the exact nature and location of the proposed impact or explosion remain unclear, alleged evidence for the fallout comes from multiple sites across North America and a site in Belgium. At 6 of the 10 original sites (excluding the Carolina Bays), elevated concentrations of various "impact markers" were found in association with black mats that date to the onset of the Younger Dryas. Black mats are common features in paleowetland deposits and typically represent shallow marsh environments. In this study, we investigated black mats ranging in age from approximately 6 to more than 40 ka in the southwestern United States and the Atacama Desert of northern Chile. At 10 of 13 sites, we found elevated concentrations of iridium in bulk and magnetic sediments, magnetic spherules, and/or titanomagnetite grains within or at the base of black mats, regardless of their age or location, suggesting that elevated concentrations of these markers arise from processes common to wetland systems, and not a catastrophic extraterrestrial impact event.

Tetrachlorocarbonyliridates: water-soluble carbon monoxide releasing molecules rate-modulated by the sixth ligand.

A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR, NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 µM min(-1) in a 10 µM solution of myoglobin and 10 µM of the complexes.

Braquiterapia endobrônquica com alta taxa de dose no tratamento paliativo do câncer do pulmão / High-dose-rate endobronchial brachytherapy for palliative treatment of lung cancer

Tumores localmente avançados como forma de apresentação inicial dos tumores localizados na árvore traqueobrônquica não são um fenômeno raro. Os sintomas resultantes dessas lesões são comuns de câncer do pulmão e têm um impacto negativo significativo na qualidade de vida dos pacientes portadores de neoplasias pulmonares. As opções terapêuticas são múltiplas, sendo no entanto dependentes de variáveis, como a terapêutica inicial utilizada, o local da recorrência, a sintomatologia e as condições clínicas dos pacientes. Os objetivos principais foram demonstrar as principais vantagens terapêuticas da braquiterapia endobrônquica com alta taxa de dose em tumores da árvore respiratória. No período de 1998 a 2009, 42 pacientes com neoplasia pulmonar foram tratados paliativamente com braquiterapia endobrónquica com alta taxa de dose, com um total de 110 inserções, no Instituto Nacional de Câncer, Rio de Janeiro. A regressão endoscópica completa do tumor foi observada em 75% dos pacientes. A regressão tumoral teve relação direta com a melhora dos sintomas, especialmente da dispnéia. A sobrevida global foi de 56%, em 15 meses de acompanhamento. Não houve nenhum caso de hemoptise volumosa ou fatal, fistulas ou abscessos. Desse modo, concluimos que a braquiterapia endobrônquica com alta taxa de dose, é um excelente método com tratamento paliativo para os pacientes portadores de neoplasias pulmonares obstrutivas.

Locally advanced tumors as the initial form of presentation of tumors in the tracheobronchial tree are not a rare event. Symptoms resulting from these tumors are common in lung cancer and have a significant negative impact on quality of life of patients with lung cancer. The therapeutic options are manifold, but being dependent on variables such as the initial therapy used, the site of recurrence, the symptoms and the clinical condition of patients. The main objectives were to demonstrate the main advantages of brachytherapy treatment with high dose rate in tumors of the respiratory tree. In the period 1998-2009, 42 patients with lung cancer were treated with brachytherapy palliatively with high dose rate, with a total of 110 insertions, at the National Cancer Institute, Rio de Janeiro. The endoscopic complete tumor regression was observed in 75% of patients. The tumor regression was directly related to improvement of symptoms, especially dyspnea. Overall survival was 56% in 15 months monitoring. There were no cases of massive or fatal hemoptysis, fistulae or abscess. Thus, we conclude thatbrachytherapy with high dose rate, is an excellent method to palliative treatment for patients with obstructive lung cancers.

Iridium, platinum and rhodium baseline concentration in lichens from Tierra del Fuego (South Patagonia, Argentina).

Lichen samples of Usnea barbata were used as possible biomonitors of the atmospheric background level of iridium (Ir), platinum (Pt) and rhodium (Rh) in the remote region of Tierra del Fuego (South Patagonia, Argentina). Lichens were collected in 2006 at 53 sites covering 7 different areas of the region (24 transplanted lichens of the northern region and 29 native lichen samples of the central-southern region). A microwave acidic digestion procedure was used to mineralize the samples and a sector field inductively coupled plasma mass spectrometry method was developed to quantify the elements. The study of the influence of interferences on analyte signals and a quality control procedure were carried out. The analytical protocol was further applied to evaluate Ir, Pt and Rh bioaccumulation in lichens. The detection limits obtained were 0.010 ng g⁻¹, 0.013 ng g⁻¹ and 0.030 ng g⁻¹ for Ir, Pt and Rh, respectively. Recoveries at different fortification levels were between 96.3% and 106% and precision was 3.3% on average. The metals concentration (as dry weight) spanned the following ranges: Ir, <0.010-1.011 ng g⁻¹; Pt, 0.016-2.734 ng g⁻¹; and Rh, 0.063-1.298 ng g⁻¹. Data on 7 areas were similar suggesting that no specific source, for example traffic or anthropogenic activity, influenced directly the metal concentrations in Tierra del Fuego. Values detected are more likely influenced by the long-range atmospheric transport of these pollutants and, in comparison with densely populated areas in the world, they can represent the baseline for low impacted areas.

Core conversion reactions of the cubane-type metal-sulfido clusters: shape shift, contraction, and expansion of the MM'Re2S4 Cubanes (M = Ir, Rh, Ru; M' = Pt, Pd).

Treatment of incomplete cubane-type clusters [(Cp*M){Re(L)}(2)(mu(3)-S)(mu(2)-S)(3)] (M = Ir (1a), Rh (1b); Cp* = eta(5)-C(5)Me(5); L = S(2)C(2)(SiMe(3))(2)) and [{(Pmb)Ru}{Re(L)}(2)(mu(3)-S)(mu(2)-S)(3)] (Pmb = eta(6)-C(6)Me(5)H) with 1 equiv of [Pt(PPh(3))(3)] gave tetranuclear tetra(sulfido) clusters having raft-type cores, [(Cp*M){Pt(PPh(3))(2)}{Re(L)}(2)(mu(3)-S)(4)] (M = Ir (3a), Rh) and [{(Pmb)Ru}{Pt(PPh(3))(2)}{Re(L)}(2)(mu(3)-S)(4)], which presents a sharp contrast to the reactions with [Pd(PPh(3))(4)] reported previously, affording the cubane-type clusters [(Cp*M){Pd(PPh(3))}{Re(L)}(2)(mu(3)-S)(4)] (M = Ir (2a), Rh) and [{(Pmb)Ru}{Pd(PPh(3))}{Re(L)}(2)(mu(3)-S)(4)]. The reactions of 2a with diphosphines P2 resulted in the conversion of its cubane-type core into the analogous raft-type frameworks, forming [(Cp*Ir){Pd(P2)}{Re(L)}(2)(mu(3)-S)(4)] (P2 = cis-Ph(2)PCH=CHPPh(2) (6), Ph(2)PCH(2)CH(2)PPh(2), Ph(2)PCH(2)CH(2)CH(2)PPh(2)). On the other hand, when 2 was allowed to react with Ph(2)PCH(2)PPh(2) (dppm) as P2, the trinuclear tri(sulfido) cluster [(Cp*Ir){Re(L)}(2)(mu(3)-S)(2)(mu(2)-S)(mu(2)-dppm)] (9a) was obtained. Alternatively, this cluster 9a and its Rh analogue 9b were derived from the incomplete cubane-type clusters 1a and 1b by treatment with dppm. It has also been found that further treatment of the cubane-type cluster 2a with excess [Pd(PPh(3))(4)] affords the heptanuclear tetra(sulfido) cluster [(Cp*Ir){Pd(PPh(3))}(4)Re(2)(mu(3)-L)(2)(mu(3)-S)(4)] (10). The detailed structures have been determined by the X-ray analyses for 3a, 6, 9a, and 10.

Correction of structured molecular background by means of high-resolution continuum source electrothermal atomic absorption spectrometry--determination of antimony in sediment reference materials using direct solid sampling.

A simple, fast and accurate procedure is proposed for the determination of antimony in certified sediment reference materials using direct solid sampling high-resolution continuum source electrothermal atomic absorption spectrometry and iridium as a permanent modifier. The less sensitive resonance line at 231.147 nm has been used in order to allow the introduction of larger sample mass. Six certified reference materials, one river, one estuarine and four marine sediments have been analyzed. The use of iridium as a permanent modifier caused an increase of 30% in sensitivity and stabilized antimony in the sediment to a pyrolysis temperature of 1100 degrees C. Significant background absorption with pronounced rotational fine structure was observed at the optimum atomization temperature of 2100 degrees C, which coincided with the analyte atomic absorption in time. This background was found to be due to the electron excitation spectra of mostly the SiO and in part the PO molecules, and could be eliminated by applying a least-squares background correction algorithm. A characteristic mass of 28 pg Sb was obtained, and the limit of detection (3sigma, n=10) was 0.02 microg g(-1), calculated for 0.2 mg of sample. The results obtained for six certified reference materials with concentrations between 0.40 and 11.6+/-2.6 microg g(-1) Sb were in agreement with the certified values according to a Student's t-test for a 95% confidence level, using aqueous standards for calibration. The precision, expressed as relative standard deviation, ranged between 7% and 17% (n=5).