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.

Geração do conhecimento através da especificação de produtos químicos

Technological innovation connects competitiveness and knowledge. In Brazil, knowledge is mainly concentrated in the universities which undertake R&D. This article aims to show the importance of Brazilian university extension activities, which transfer knowledge to society, contributing, in the case of the chemical sector, to a reduction in the country's total trade deficit of around US$8.5 billion, which is result of the importation of innumerable products. On the other hand, developed countries are resorting to technical barriers, which impose documentation and regulations based on testing products for conformity with standards. This demands a technical and scientific infrastructure, concentrated in the universities.

Estresse oxidativo: relação entre geração de espécies reativas e defesa do organismo

This work describes the mechanism of action of some reactive oxygen species (ROS) and reactive nitrogen species (RNS) in the oxidative stress of the human body, and their consequences on damage to DNA, RNA, proteins and lipids. It also illustrates the defense system of our organism against these ROS and RNS species. The action of nonenzymatic protection systems is reported, with emphasis on micromolecules like Q10 coenzyme, vitamin C, alpha-tocopherol, carotenoids and flavonoids. The importance of flavonoids is also emphasized, and their body protection mechanism is detailed.

Oxidação de proteínas por oxigênio singlete: mecanismos de dano, estratégias para detecção e implicações biológicas

Proteins are potential targets for singlet molecular oxygen (¹O2) oxidation. Damages occur only at tryptophan, tyrosine, histidine, methionine, and cysteine residues at physiological pH, generating oxidized compounds such as hydroperoxides. Therefore, it is important to understand the mechanisms by which ¹O2, hydroperoxides and other oxidized products can trigger further damage. The improvement and development of new tools, such as clean sources of ¹O2 and isotopic labeling approaches in association with HPLC/mass spectrometry detection will allow one to elucidate mechanistic features involving ¹O2-mediated protein oxidation.

Sensores eletroquímicos: considerações sobre mecanismos de funcionamento e aplicações no monitoramento de espécies químicas em ambientes microscópicos

Electrochemical sensors have attracted considerable attention in recent years because they provide data about the chemical state of our surroundings and the dynamics of the chemical transformations in the form a spatially resolved image. Particular interest has been directed to measurements in restricted-volume samples as new technologies enable the fabrication of miniaturized versions of sensors with reproducible characteristics. Taking these aspects into consideration, this review focuses on the use of electrodes of micrometer dimensions to acquire chemical information in microdomains in which concentrations may not be spatially homogeneous. This is possible because microelectrodes allow fast-response measurements with micrometer resolution to be performed. On the other hand, the use of microelectrodes as amperometric sensors presents an inherent drawback owing to the insufficient specificity toward the substrate of interest. Hence, some comments on strategies to enhance the selectivity of amperometric sensors are also made. Finally, recent applications of structurally microscopic electrodes as in vivo sensors are shown, as well as a prospect of the future trend in this field.

Produção biotecnológica de poli-hidroxialcanoatos para a geração de polímeros biodegradáveis no Brasil

In recent years, several studies have been developed in Brazil to produce biodegradable materials. A particular family of bacterial polymers, the polyhydroxyalkanoates (PHA), has received special attention. PHAs are thermoplastic, biodegradable, biocompatible, are synthesised from renewable resources and can substitute petrochemical plastics in some applications. Different aspects have been focused to increase productivity and to reduce the cost of PHA production: bacterial improvement, use of industrial by-products as raw material, bioreactor design, process operation strategies, downstream process, mathematical modelling, polymer characterisation, application and biodegradability of blends. A production process was transferred to industry and studies to produce new PHA by controlling monomer composition are in progress. All these aspects are presented in this review.

Uso da cinza da casca do arroz (CCA) obtida da geração de energia térmica como adsorvente de Zn(II) em soluções aquosas

The removal study was conducted using 1.00 g of the rice husk ash (RHA) and 20.0 mL solution with concentrations in the range of 10-1000 mg/L of Zn(II). The influence of contact time, initial metal concentration, agitation and pH of the removal process was investigated. Superior removals to 95% were obtained at the end of 24 h of contact. The agitation increased in 20% the removal of Zn(II), being needed only 5 min to reach the equilibrium. The adsorption process was studied by the models of isotherms of Langmuir, Freundlich and BET, obtaining results of R L and 1/n for a process favorable of adsorption. BET isotherm best represents the equilibrium adsorption. The results showed that the RHA has the largest capacity and affinity for the removal of Zn(II).

Mecanismos químicos e mineralógicos de transformação da magnesioferrita de solo derivado de tufito, da região do Alto Paranaíba, MG

Magnetic soils forming on tuffite of the region of Alto Paranaíba, Minas Gerais, Brazil, usually contain iron-rich spinels exceptionally rich in magnesium and titanium. In this work, samples of the magnetically separated portion from the sand fraction of a Brunizém (Chernossolo) and from its mother-rock material were analyzed with synchrotron X-ray diffraction and 57Fe-Mössbauer spectroscopy. Magnesioferite (MgFe2O4) and maghemite (its pure non-stoichiometric spinel structure, Fe8/3 ⊕ 1/3 O4, where ⊕ = cation vacancy, corresponds to γFe2O3) were the magnetic iron oxides so identified. Basing on these data, a consistent chemical-mineralogical model is proposed for the main transformation steps involving these iron oxides in the pedosystem, starting on magnesioferrite to finally render hematite (αFe2O3), passing through maghemite as an intermediate specie.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Validação de metodologia analítica para determinação de mercúrio total em amostras de urina por espectrometria de absorção atômica com geração de vapor frio (CV-AAS): estudo de caso

Mercury is a toxic metal used in a variety of substances over the course history. One of its more dubious uses is in dental amalgam restorations. It is possible to measure very small concentrations of this metal in the urine of exposed subjects by the cold vapor atomic absorption technique. The present work features the validation as an essential tool to confirm the suitability of the analytical method chosen to accomplish such determination. An initial analysis will be carried out in order to evaluate the environmental and occupational levels of exposure to mercury in 39 members of the auxiliary dental staff at public consulting rooms in the city of Araguaína (TO).

Tintas anti-incrustantes de terceira geração: novos biocidas no ambiente aquático

Antifouling agents have been used on vessels and boats since ancient civilizations. Thus, a brief history on the three generations of antifouling paints was provided in the present review. Additionally, information about physic-chemical properties, environmental levels, toxicology and analytical methods was discussed for the 16 "new" booster biocides used as third-generation antifouling paints. The main problems, limitations and future trends related to this subject were also presented. Finally, actions were suggested in order to appraise the current status of the environmental impact caused by these compounds in South America.

Do engenho à biorrefinaria: a usina de açúcar como empreendimento industrial para a geração de produtos bioquímicos e biocombustíveis

A sugar cane mill is at the present moment a modest biorefinery producing few products such as sugar, ethanol and polyhydroxybutyrate (PHB). In the near future, this mill can expand its production using several renewable feedstock's to produce biofuels and high value biobased chemicals. However, the choice of appropriate products for addition to the portfolio is challenged by a lack of broad-based conversion technology coupled with a plethora of potential targets. The intent of this revision was to catalyze research efforts to expand the list of products and to present an updated evaluation of potential target structures for chemical production.

Mecanismos envolvidos na biodegradação de materiais lignocelulósicos e aplicações tecnológicas correlatas

The biodegradation of lignocellulosic materials is an important natural process because it is responsible for the carbon recycling. When induced under controlled conditions, this process can be used for technological applications such as biopulping, biobleaching of cellulosic pulps, pre-treatment for subsequent saccharification and cellulosic-ethanol production, and increase of the digestibility in agroindustrial residues used for animal feed. In the present work, the enzymatic and non-enzymatic mechanisms involved in the biodegradation of lignocellulosic materials by fungi were reviewed. Furthermore, the technological applications of these extracellular metabolites are presented and discussed.

Geração de mesoporos em zeólitas ZSM-5 e seus efeitos na conversão do etanol em olefinas

Developing mesoporosity in HZSM-5 zeolites is an alternative for improving their catalytic performance on chemical reactions. In this work, alkaline and thermal treatments were used to produce mesoporosity. These treatments increased mesoporous area and volume. They also influenced the acid properties of the samples. Concerning catalytic performance, treatments modified reaction product distribution. Whereas alkaline treatment favored formation of olefins and increased propene ratio in the beginning of the reaction, thermal treatment resulted in formation of only ethylene due to the low acidity of the sample.

Estudo por espectrometria de massas de soluções de hidróxi(tosilóxi)iodobenzeno: propostas para mecanismos de desproporção

Solutions of [hydroxy(tosyloxy)iodo]benzene (HTIB or Koser's reagent) in acetonitrile were analyzed using high resolution electrospray ionization mass spectrometry (ESI-MS) and electrospray ionization tandem mass spectrometry (ESI-MS/MS) under different conditions. Several species were characterized in these analyses. Based on these data, mechanisms were proposed for the disproportionation of the iodine(III) compounds in iodine(V) and iodine(I) species.