Oxidações catalíticas e eletrocatalíticas de substratos orgânicos. O cério como oxidante

This paper reviews the catalytic and electrocatalytic oxidation of organic compounds using cerium (IV) salts. Direct and indirect methods and those using modified electrodes are described.

Coordenação local do Eu(III) em híbridos orgânicos/inorgânicos emissores de luz branca

Eu3+ luminescence and EXAFS (Extended X-ray Absorption Fine Structure) results are presented for organic-inorganic hybrid gel hosts composed of a siliceous network to which small chains of oxyethylene units are covalently grafted by means of urea bridges. Coordination numbers for Eu3+ ions range from 12.8 to 9.7 with increasing Eu3+ concentration while the Eu3+-first neighbours mean distance is found to be constant at 2.48-2.49 Å in the same concentration range. Emission spectra display a broad band in the green/blue spectral region superposed to narrow lines appearing in the yellow/red region in such a way that for the eyes emission appears white. The broad band is assigned to intrinsic NH groups emission and also to electron-hole recombination in the nanosised siliceous domains. The narrow lines are assigned to intra-4f6, 5D0->7F0-4 Eu3+ transitions and from the energy position of the 7F0-4 levels a mean distance could be calculated for the Eu3+-first neighbours. The calculated results are in good agreement with the experimental ones obtained from EXAFS analysis.

Estudo de compostos orgânicos em lixiviado de aterros sanitários por EFS e CG/EM

The main purpose of this work was the qualitative study of organic compounds in landfill leachate. The samples were collected from a sanitary landfill located at Gravataí, a southern Brazilian city, that receive both, industrial and domestic refuse. The samples were submitted to solid phase extraction (SPE) with XAD-4 resin as the stationary phase. The instrumental analysis was performed by Gas Chromatography with a Mass Spectrometry Detector (GC/MSD). The compounds achieved in the SPE extracts were tentatively identified by the GC/MS library. It was found several oxygen and nitrogen compounds like carboxylic acids, ketones, amines and amides. Sulfur compounds and phthalate esters are also identified.

Quimiluminescência de peróxidos orgânicos: geração de estados eletronicamente excitados na decomposição de 1,2-dioxetanos

In this review article, we give a general introduction on the mechanisms involved in organic chemiluminescence, where three basic models for excited state formation are presented. The chemiluminescence properties of 1,2-dioxetanes - four membered ring peroxides - are briefly outlined in the second part. In the main part, the mechanisms involved in the decomposition of 1,2-dioxetanes and analogous peroxides are discussed: (i) the unimolecular decomposition of 1,2-dioxetanes; (ii) the electron transfer catalyzed decomposition of peroxides by an intermolecular CIEEL (Chemically Initiated Electron Exchange Luminescence) mechanism; (iii) 1,2-dioxetane decomposition catalyzed by an intramolecular electron transfer mechanism (intramolecular CIEEL). Special emphasis is given to the latter subject, where recent examples with potential analytical applications are presented.

Exposição ocupacional a compostos orgânicos voláteis na indústria naval

The scope of this study involved the evaluation of the concentration of some volatile organic compounds in the internal environmental air of a naval shipyard in the State of Rio de Janeiro, during painting activities in enclosed, semi-enclosed and open areas. Xylene was the volatile compound found in greatest abundance (25.20 to 191.66 ppm) in the locations researched. Benzene in the air, which is a carcinogenic substance, attained levels of 3.34 ppm in semi-enclosed environments and the highest levels of toluene, xylene and n-butanol were found in the enclosed space of the ship. Results obtained highlight the need to establish air quality control programs in these internal areas, in order to safeguard the health of the workers.

Descoloração e degradação de poluentes orgânicos em soluções aquosas através do processo fotoeletroquímico

Organic compounds responsible for the color of wastewaters are usually refractory to biological digestion. In this paper the photo-assisted electrolysis process is used for color removal from three of the most colored wastewaters, which are daily generated in large amounts: the E1 bleach Kraft mill effluent, a textile reactive dye effluent and a landfill leachate. Electrolysis was carried out at 26,5 mA cm-2 in a flow reactor in which the anode surface was illuminated by a 400 W high pressure Hg bulb. In all experiments 70-75% of color reduction was observed which was also followed by a net organic load oxidation.

Compostos orgânicos em sedimentos marinhos: uma viagem ao fundo do Oceano Atlântico Norte

The present study investigates the origin and distribution of several classes of organic compounds present in recently deposited abyssal sediments in the North East Atlantic Ocean. Six cores were sampled (multicorer) along 20ºW longitude as part of the UK's Biogeochemical Ocean Flux Study (BOFS). The sediments underlie diverse water columns, ranging from the Iceland Basin, an area of high primary productivity but presumed low aeolian inputs, to an area off West Africa characterized by oligotrophic and upwelling waters and high aeolian input. Concentration of predominantly marine (e.g. sterols and alkenones) and terrestrial (n-alkanes) compounds showed remarkable changes along the transect.

Bastões de grafite reciclados de baterias comuns e seu uso como eletrodo modificado em hidrogenação eletrocatalítica de alguns substratos orgânicos

This paper presents some results on the employ of recycled graphite electrode obtained from used common 1.5 V batteries in the preparation of modified electrode and the electrocatalytical hydrogenation of benzaldehyde and of n-valeraldehyde. This inexpensive and easy to obtain electrode was prepared by coating it with a 1:1 mixed film of poly-(allylfenil ether): poly-[allyl p-(2-ethylammonium) benzene ether] and introduction of dispersed platinum particles by ion exchange and reduction of PtCl4-2. Electroreduction of H+ from aqueous H2SO4 using the proposed electrode hydrogenated the substrates in a way comparable with that of vitreous carbon electrode.

Híbridos inorgânico-orgânicos derivados da reação de filossicatos com organossilanos

Silylation reactions involving hydroxylated surfaces are an important route for synthesis of new materials that could present selected properties, for application in different areas such as catalysis, chromatography, adsorption and electrochemistry. An overview of many synthetic routes, comprising organosilanes to yield phyllosilicates is now presented.

Hidrogenação de compostos orgânicos utilizando método eletroquímico para geração de hidrogênio in situ: hidrogenação eletrocatalítica

Electrocatalytic hydrogenation (HEC) may be compared to catalytic hydrogenation (HC). The difference between these methods is the hydrogen source: HC needs a hydrogen gas supply; HEC needs a source of protons (solvent) to be reduced at a cathode surface. HEC has presented interesting advances in the last decades due to investigation of the influence of the supporting electrolyte, co-solvent, surfactant, presence of inert gas and the composition of the electrode on the reaction. Several classes of organic compounds have been hydrogenated through HEC: olefins, ketones, aldehydes, aromatics, polyaromatics and nitro-compounds. This paper shows some details about the HEC which may be regarded as a promising technique for the hydrogenation of organic compounds both in industrial processes and in laboratories.

Hidrogenação eletrocatalítica de substratos orgânicos: estudo da eficiência dos metais nobres níquel, paládio e platina usando eletrodos modificados

Nickel, palladium and platinum micro-crystals were dispersed in films covering a vitreous carbon plate electrode by ion exchange followed by electroreduction of their ions. These modified electrodes were used in the electrocatalytic hydrogenation of several substrates of different classes and their efficiency is reported. A comparison among them was performed based on the structural characteristics of the metals. A modified electrode containing platinum showed to be more efficient than a palladium modified electrode and the one of nickel was the less efficient.

Ferro zero: uma nova abordagem para o tratamento de águas contaminadas com compostos orgânicos poluentes

Anthropogenic pollution of groundwater and surface water has become a very serious environmental problem around the world. A wide range of toxic pollutants is recalcitrant to the conventional treatment methods, thus there is much interest in the development of more efficient remediation processes. Degradation of organic pollutants by zero-valent iron is one of the most promising approaches for water treatment, mainly because it is of low cost, easy to obtain and effective. After a general introduction to water pollution and current treatments, this work highlights the advances, applications and future trends of water remediation by zero-valent iron. Special attention is given to degradation of organochloride and nitroaromatic compounds, which are commonly found in textile and paper mill effluents.

Extração no ponto nuvem de compostos orgânicos homólogos e isômeros

In this work, the feasibility of employing micelle-mediated extraction for selective separation of homologous or isomeric organic compounds is demonstrated. Firstly, the main parameters controlling extraction performances, such as surfactant concentration and temperature were varied. A Scheffé-type experimental design was demonstrated as a novel and useful method to characterize the various experimental factors. At each point selected in the two-phase domain and for a given solute, extraction percentage (E%), concentration ratio, phase volume ratio, and equilibrium partition coefficient (K C) were determined. The values of E% and K C decrease in the following order: phenol > 1-phenylethanol ~ 2-phenylethanol > benzyl alcohol.

Amostragem de compostos orgânicos voláteis no ar utilizando a técnica de microextração em fase sólida

The sampling of volatile organic compounds using solid phase microextraction is reviewed and its principles are described. The development and application of solid phase microextraction in the sampling of VOCs are presented and discussed.

A reação de metátese de olefinas: reorganização e ciclização de compostos orgânicos

The olefin metathesis reaction allows the exchange of complex alkyl units between two olefins, with the formation of a new olefinic link and a sub-product olefin usually ethylene. This reaction has found extensive application in the last ten years with the development of the Grubbs and Schrock catalysts, in total synthesis of complex organic molecules, as opposed to the very important use in the petrochemical industry with relatively simple molecules. This review intends to trace a historical and mechanistic pathway from industry to academy, before illustrating the more recent advances.