Utilização do TEMPO (N-oxil-2,2,6,6-tetrametilpiperidina) na oxidação de álcoois primários e secundários

The oxidation of alcohols to obtain ketones, aldehydes or carboxylic acids is a fundamental transformation in organic synthesis and many reagents are known for these conversions. However, there is still a demand for mild and selective reagents for the oxidation of alcohols in the presence of other functional groups. As an alternative, the nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) has been demonstrated to be a useful reagent for the transformation of alcohols. The oxidation of alcohols using TEMPO is often efficient, fast, selective, made in mild conditions and can tolerate sensitive functional groups. In this article we report different methodologies using TEMPO in the oxidation of alcohols.

Myoglobins: the link between discoloration and lipid oxidation in muscle and meat

Aerobic metabolism changes rapidly to glycolysis post-mortem resulting in a pH-decrease during the transformation of muscle in to meat affecting ligand binding and redox potential of the heme iron in myoglobin, the meat pigment. The "inorganic chemistry" of meat involves (i) redox-cycling between iron(II), iron(III), and iron(IV)/protein radicals; (ii) ligand exchange processes; and (iii) spin-equilibra with a change in coordination number for the heme iron. In addition to the function of myoglobin for oxygen storage, new physiological roles of myoglobin are currently being discovered, which notably find close parallels in the processes in fresh meat and nitrite-cured meat products. Myoglobin may be characterized as a bioreactor for small molecules like O2, NO, CO, CO2, H2O, and HNO with importance in bio-regulation and in protection against oxidative stress in vivo otherwise affecting lipids in membranes. Many of these processes may be recognised as colour changes in fresh meat and cured meat products under different atmospheric conditions, and could also be instructive for teaching purposes.

Anéis aromáticos condensados e relação E4/E6: estudo de ácidos húmicos de gleissolos por RMN de 13C no estado sólido utilizando a técnica CP/MAS desacoplamento defasado

In this work, seven samples of humic acids extracted from gleysoils were investigated. These studies, using NMR CP/MAS 13C techniques, did not show significant correlation between the E4/E6 ratio and the degree of aromaticity. However, dipolar dephasing (DD) measurements of condensed aromatic or substituted carbons showed a negative correlation of 0.94. Also, there was a good correlation between the amount of semiquinone free radicals measured by the EPR technique and condensed aromatic rings measured by NMR CP/MAS 13C with the DD technique. The content of semiquinone free radicals was quantified by EPR spectroscopy and was correlated with the humification (degree of aromaticity) of the humic substances. The results indicated that the E4/E6 ratio identifies the degree of aromatic rings condensation. It was also found that the degree of aromaticity, measured by NMR, as frequently presented in the literature (by conventional CP/MAS), underestimates aromatic rings in condensed structures.

Carotenóides: propriedades, aplicações e biotransformação para formação de compostos de aroma

Carotenoids are widely distributed in nature, providing yellow, orange or red color in a great number of vegetables, microorganisms and in some animals. Carotenoids act as biological antioxidants and seem to play an important role in human health by protecting cells and tissues from the damaging effects of free radicals and singlet oxygen. Several authors describe the oxidative cleavage of carotenoids in flavor compounds as occuring through chemical or photochemical degradations or through biotechnological processes. Biotransformation of carotenoids seems to be a reasonable alternative to produce flavor compounds since these compounds are considered 'natural' ingredients. In this work we describe the properties of some carotenoids, as well as biotechnological approaches to obtain its oxyfunctionalized derivatives.

Mecanismo e aplicações da reação de fenton assistida por compostos fenólicos redutores de ferro

The mechanism and applications of the Fenton reaction assisted by iron-reducing phenolic compounds (IRPC) is reviewed. The presence of IRPC leads to the formation of a larger number of free radicals. The relationship between the redox potential and the IRPC structure is discussed. The effect of humic substances in the degradation of xenobiotics is also included, since these substances are able to reduce metallic ions. The natural occurrence of Fe3+/H2O2/IRPC in wood biodegradation processes, as well as their application is also discussed. The review concludes with the advantages of the Fe3+/H2O2/IRPC systems and some considerations for further process optimization and their applications at industrial levels.

Plasma polymerized acetaldehyde thin films for retention of volatile organic compounds

The aim of this work is the production and characterization of plasma polymerized acetaldehyde thin films. These films show highly polar species, are hydrophilic, organophilic and easily adsorb organic reactants with CO radicals but only allow permeation of reactants with OH radicals. The good step coverage of films deposited on aluminum trenches is useful for sensor development. Films deposited on hydrophobic substrates may result in a discontinued layer, which allows the use of preconcentration in sample pretreatment. Deposition on microchannels showed the possibility of chromatographic columns and/or retention system production to selectively detect or remove organic compounds from gas flows.

Avaliação do potencial antioxidante de extratos ativos de plantas obtidos por extração com fluido supercrítico

The aim of this work was to evaluate the antioxidant properties of ginger and rosemary extracts, obtained by supercritical extraction. The extracts were characterized by HPLC, GC-MS, phenolic compounds content and antioxidant activity. The main active compounds were identified and high content of phenolic compounds was observed. The extracts presented high antioxidant activity against the free radicals ABTS•+ (350 and 200 mM Trolox/g, for ginger and rosemary, respectively) and DPPH•+ (145 and 80 mM Trolox/g, for ginger and rosemary, respectively). These results suggested that the attained extracts are potential substitutes of synthetic antioxidants used in chemical, food and pharmaceutical industries.

Importance of the lipid peroxidation biomarkers and methodological aspects FOR malondialdehyde quantification

Free radicals induce lipid peroxidation, playing an important role in pathological processes. The injury mediated by free radicals can be measured by conjugated dienes, malondialdehyde, 4-hydroxynonenal, and others. However, malondialdehyde has been pointed out as the main product to evaluate lipid peroxidation. Most assays determine malondialdehyde by its reaction with thiobarbituric acid, which can be measured by indirect (spectrometry) and direct methodologies (chromatography). Though there is some controversy among the methodologies, the selective HPLC-based assays provide a more reliable lipid peroxidation measure. This review describes significant aspects about MDA determination, its importance in pathologies and biological samples treatment.

Propriedades redox da matéria orgânica isolada de material ultrafiltrado das águas do rio Paraíba do Sul

Previous studies indicated that free radicals control organic matter redox activities. In the present study, organic matter of an ultra-filtrated material collected from seven samples taken seasonally from the Paraiba do Sul River for two years were titrated with an oxidizer (I2) in an inert atmosphere. Standard formal potential values for the electrode MO Ox, MO Red ranged from 0.754 to 0.786 V at a 25 ºC temperature. Organic matter oxidation capacity (COx) per carbon mass varied according to pH values, and changes in COx were related to rainfall and river flow intensities.

Aspectos mecanísticos da bioatividade e toxicidade de nitrocompostos

Nitrocompounds are bioactive molecules used as antibacterial, antiparasitic and antitumoral agents. In the past of years, these molecules have been broadly studied in several fields, such as medicinal chemistry, organic chemistry, biochemical, toxicology and electrochemistry. The nitrocompounds mode of action involves the biotransformation of the nitro group, releasing intermediates in the redox process. Some of those intermediates attack enzymes, membranes and DNA, providing the basis for their biological activity and adverse effects. In this report, some aspects regarding the biological activity, mechanism of action and toxicity of nitrocompounds are explored, purposing the research of new bioactive derivatives having low toxicity.

Nanoestruturas em fotocatálise: uma revisão sobre estratégias de síntese de fotocatalisadores em escala nanométrica

Advanced oxidative processes (AOPs) are based on chemical processes that can generate free radicals, such as hydroxyl radicals (.OH) which are strong, non-selective oxidant species that react with the vast majority of organic compounds. Nanostructured semiconductors, especially titanium dioxide (TiO2) in the anatase phase, are well-established photocatalysts for this process, which have proved to be useful in the degradation of dyes, pesticides and other contaminants. Research in different strategies for the synthesis of nanostructured semiconductors, with particular characteristic is currently a topic of interest in many studies. Thus, this paper presents a review about various synthesis strategies of nanostructured photocatalysts.

Interferência da lignina na quantificação de radicais livres no processo de compostagem

In this work was studied composts and their humic acids (HA) to evaluate the use of EPR in the monitoring of the humification. It was observed increase in the concentration of organic free radical (OFR) in all the composts, but in L1 the increase was more significant than L2 and L3. Research more detailed of L1 showed that the lignin is main source of OFR. Then determination of these radicals in material in nature that contains high amount of lignin isn't a good indicator to monitor the humification process in the composting and yes the fraction HA of the composts.

Spectroscopic characterization of schiff base-copper complexes immobilized in smectite clays

Herein, the immobilization of some Schiff base-copper(II) complexes in smectite clays is described as a strategy for the heterogenization of homogeneous catalysts. The obtained materials were characterized by spectroscopic techniques, mostly UV/Vis, EPR, XANES and luminescence spectroscopy. SWy-2 and synthetic Laponite clays were used for the immobilization of two different complexes that have previously shown catalytic activity in the dismutation of superoxide radicals, and disproportionation of hydrogen peroxide. The obtained results indicated the occurrence of an intriguing intramolecular redox process involving copper and the imine ligand at the surface of the clays. These studies are supported by computational calculations.

Electrocatalysis in wastewater treatment: recent mechanism advances

Over 50 years, several scientists and industries have developed new alternatives for wastewater treatment and remediation. Recently, electrochemical technology has been largely developed mainly because of its versatility and environmental compatibility. Scientific contributions about role of the electrode material have allowed determining that the influence of material in the selectivity is an important parameter. However, to interpret this behavior, comprehensive physical chemistry models for organics destruction, related to electrochemical phenomena and material surfaces, were proposed in the last decades. So, this paper presents a critical and comprehensive review about the principles and recent mechanism advances in electrocatalysis for wastewater treatment.

Antioxidant activities of isolated compounds from stems of Mimosa invisa Mart. ex Colla

This work describes the phytochemical study of stems of Mimosa invisa (Mimosaceae) and the evaluation of the antioxidant potential of isolated compounds. Cromatografic techniques were employed to isolate salicifoliol, pinoresinol, quercetin, quercetin-3-O-rhamnopyranosyl, quercetin-3-O-arabinofuranosyl lupeol, β-amyrin, sitosterol, p-hydroxy coumaric acid, 4-hydroxy-3-methoxy benzaldehyde (vanillin), 4-hydroxy-3,5-dimethoxy benzaldehyde, 4-hydroxy-3-methoxy benzoic acid and 4',6,7- trimethoxy flavonol. The latter had been previously described but the spectrometric data shown indicated the structure required review. The antioxidant activity of the compounds was evaluated by the DPPH test and capability of NBT reduction by superoxide radicals. Quercetin glycosides showed lower antioxidant potential than quercetin and, salicifoliol was found to be more active than pinoresinol.