Otimização de um mecanismo fotoquímico para a simulação da atmosfera urbana brasileira

A photochemical reaction mechanism for the description of air quality in Brazilian urban regions is described and evaluated by comparison with chamber experiments. The mechanism was developed for use in ozone modeling and application of control strategies. The oxidation of ethanol and methyl-ter-butyl-ether is also considered. Using this chemical model, a trajectory simulation of Brazil Avenue, Rio de Janeiro, was performed. The model predicts that ozone should reach a maximum of 22.4 ppb at 14:57 h. This value is in good agreement with the experimental measurements of 22.5 ppb for 14:00 h and 22.3 ppb for 15:00 h.

A quimiluminescência como ferramenta analítica: do mecanismo a aplicações da reação do luminol em métodos cinéticos de análise

Relevant aspects of proposed mechanisms of the chemiluminescent reaction of luminol are presented and commented to emphasize its perspectives for kinetic analysis. A careful search for analytical applications of this reaction is discussed in order to point out new trends of the studies. Kinetic analysis using the luminol reaction is proposed to be a very attractive due to the good performance of the reaction in analytical applications and the positive characteristics of kinetic analysis, such as low cost and sensibility. It is pointed out that kinetic analysis using the chemiluminescent reaction of luminol should be encouraged.

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.

Ácido clavulânico e cefamicina c: uma perspectiva da biossíntese, processos de isolamento e mecanismo de ação

The present article reviews different aspects of the chemistry of two widely used β-lactam antibiotics Clavulanic Acid and Cephamycin C. The article discusses important details of the biosynthesis of these compounds, their action mechanism and, principally, the methods employed in their isolation and purification, in accordance with the available literature. Despite the large quantity of available articles and patents concerning β-lactam antibiotics, those which describe the isolation and purification of Clavulanic Acid and Cephamycin C are rare. Overall, the intention of this article is to discuss the up-to-date scientific research related to the compounds under review.

Investigação do mecanismo de catálise ROMP do norborneno utilizando métodos de funcional de densidade

This work presents a density functional theory study of the norbornene ROMP metathesis reactions. The energies have been calculated in a Grubbs catalyst model Cl2(PH3)2Ru=CH2. The geometries and energy profile are similar to the Grubbs metilydene (Cl2(PCy3)2Ru=CH2 real model. It was found that the metathesis reaction proceeds via associative mechanism (catalyst-norbonene) followed by dissociative substitution of a phosphine ligand with norbonene, giving a monophosphine complex. The results are in reasonable agreement with the available experimental data. The dissociation energy of the phosphines is predicted to be 23.2 kcal mol-1.

HIV: mecanismo de replicação, alvos farmacológicos e inibição por produtos derivados de plantas

The AIDS epidemy has spread out and led to the diversification on the research for new antiviral drugs. Natural products, especially those derived from plants, are well-recognized as excellent sources of new drugs. Several of them have inhibitory activity against HIV replication, and some have been already clinically tested, with favorable results. This review presents the biochemical basis of the viral cycle and the research up to date on the identification, determination of the mechanism of biological action together with the therapeutical potential of plants-derived natural products, in the inhibition of HIV.

Interpretação do mecanismo de difusão no processo gás-sólido da reação de dessulfurização

The present paper aims to interpret the SO2 diffusion mechanism process for two different limestones: a calcite and a dolomite. In previous study, the apparent activation energies for sulfation reaction were between 3.03 and 4.45 kJ mol-1 for the calcite, and 11.24 kJ mol-1 for the dolomite. Using nitrogen porosimetry it was possible to observe that the dolomite presents mesopores of 0.03 μm, while the calcite presents mesopores of 0.01 μm. The evaluation of limestones porous structure together with their kinetic parameters, allowed concluding that the diffusion mechanism follows Fick law and Knudsen law for dolomite and calcite, respectively.

Simulação Monte Carlo de mecanismo de transferência de energia de excitação eletrônica: modelo de Perrin para a supressão estática da luminescência

A software based in the Monte Carlo method has been developed aiming the teaching of the Perrin´s model for static luminescence quenching. This software allows the student to easily simulate the luminescence decays of emissive molecules in the presence of quenching ones. The software named PERRIN was written for FreeBASIC compiler and it can be applied for systems where the molecules remain static during its excited state lifetime. The good agreement found between the simulations and the expected theoretical results shows that it can be used for the luminescence and excited states decay kinetic teaching.

Ozonólise: a busca por um mecanismo

The ozonolysis reaction is widely used in the academy and in industry. The first reports about the existence of the ozone molecule were made over 200 years ago. Several ideas and assumptions were made to understand the chemical properties of the ozone molecule and the ozonolysis mechanism. The intent of this paper is not to be an extensive review about ozone chemistry or ozonolysis reactions, but to highlight how the rational process was developed and how conclusions were drawn at a time with limited instrumentation.

Bioluminescência de fungos: distribuição, função e mecanismo de emissão de luz

The emission of light by living organisms, bioluminescence, has been studied since the nineteenth century. However, some bioluminescent systems, such as fungi, remain poorly understood. The emitter, the two enzymes involved, and the reaction mechanism have not yet been unraveled. Moreover, the ecological role and evolutionary significance for fungal luminescence is also unknown. It is hoped that comprehensive research on fungal bioluminescent systems will generate knowledge and tools for academic and applied sciences. This review discusses the distribution of bioluminescent fungi on Earth, attempts to elucidate the mechanism involved in light emission, and presents preliminary results on the evolution and ecological role of fungal bioluminescence.

Efeito da ativação mecânica de uma formulação de talco/caulim/alumina sobre o mecanismo e a cinética de formação de cordierita

In this study, the influence of mechanical activation by intensive ball milling of a stoichiometric mixture of talc, kaolin, and alumina on the mechanism and kinetics of cordierite (2MgO·2Al2O3·5SiO2) formation was evaluated. The raw materials were characterized by chemical analysis, X-ray diffraction (XRD), laser diffraction, and helium pycnometry. The kinetics and mechanism of cordierite formation were studied by XRD, differential thermal analysis, and dilatometry in order to describe the phase formation as a function of temperature (1000-1400 ºC), time of thermochemical treatment (0-4 h), and grinding time of the mixture (0-45 min). Finally, the optimal conditions of the thermochemical treatment that ensured the formation of cordierite were determined: milling time of 45 min and thermal treatment at 1280 ºC for 1 h.

Software para simulação de mecanismo de supressão da luminescência: modelo cinético de Stern-Volmer

A software that includes both Stochastic and Molecular Dynamics procedures has been developed with the aim of visualizing the Stern-Volmer kinetic mechanism of dynamic luminescence quenching. The software allows the student to easily simulate and graphically visualize the molecular collisions, the molecular speed distributions, the luminescence decay curves, and the Stern-Volmer graphs. The software named "SternVolmer" is written for the FreeBASIC compiler and can be applied to dynamic systems where luminescent molecules, during their excited state lifetimes, are able to collide with quenching molecules (collisional quenching). The good agreement found between the simulations and the expected results shows that this software can be used as an effective teaching aid for the study of luminescence and kinetic decay of excited states.

MÉTODO ALTERNATIVO PARA A SÍNTESE E MECANISMO DE 2-(1,3-DITIANO-2-ILIDENO)-ACETONITRILA

We report an alternative method for the synthesis of 2-(1,3-dithian-2-ylidene)-acetonitrile using 3-(4-chlorophenyl)-3-oxopropanenitrile and carbon disulfide as starting materials. The methanolysis of the intermediate 3-(4-chlorophenyl)-2-(1,3-dithian-2-ylidene)-3-oxopropanenitrile occurs via three possible intermediates, leading to the formation of the product at a 75% overall yield. Molecular modeling simulation of the reaction pathway using B3LYP 6-311G++(2df,2p) justified the proposed reaction mechanism.

Mecanismo genético de resistência em três cultivares de algodoeiro a Xanthomonas axonopodis pv. malvacearum

A mancha angular do algodoeiro (Gossypium hirsutum) causada por Xanthomonas axonopodis pv. malvacearum (Xam) é uma doença de importância econômica para o Brasil, e sua severidade depende de fatores climáticos e da cultivar. A doença não é controlada por produtos químicos sendo que seu controle depende da utilização de sementes sadias, e resistência varietal. DeltaOPAL, EPAMIG Liça, e Fibermax 986 são importantes fontes de resistência a Xam, pois além de resistência, apresentam boas características agronômicas. O objetivo do presente trabalho foi estudar o mecanismo de resistência à mancha angular envolvendo cruzamentos entre as três cultivares resistentes e a suscetível BRS Ita 90, em casa de vegetação. Populações parentais, F1 e F2 foram avaliadas após inoculação com um isolado agressivo de Xam. As três cultivares apresentaram mecanismos diferentes de resistência. Nas cultivares DeltaOPAL e EPAMIG Liça a resistência é conferida por um gene dominante, enquanto que em Fibermax 986, a resistência é dada por dois genes dominantes, independentes e complementares.

Determinação do mecanismo de destruição de células mediado por meso-tetramesitylporfirina, octaetilporfirina, octaetilporfirina de vanadil e luz visível

A Terapia Fotodinâmica é um tratamento clínico empregado no combate a vários tipos de tumores. Nesta técnica, o paciente recebe uma certa dosagem de uma substância fotossensibilizadora que, por sua vez, acumula-se preferencialmente no tecido tumoral. Em seguida irradia-se luz visível, neste tecido, com a finalidade de se excitar o fotossensibilizador. Esta substância, excitada, pode transferir elétrons e/ou energia para o oxigênio, no estado fundamental, gerando espécies reativas de oxigênio como o radical superóxido e oxigênio singlete. O primeiro é gerado no mecanismo tipo I, pela transferência de elétrons, e o segundo no mecanismo tipo II, pela transferência de energia. Estas espécies reativas geram um estresse oxidativo, no tecido tumoral, levando as células cancerígenas à morte. Neste trabalho, foram avaliadas as propriedades fotossensibilizadoras de três porfirinas e constatou-se que as mesmas são capazes de destruir células, na presença de luz e oxigênio. Este evento foi mais pronunciado, na presença de água deuterada, e inibido por supressores de oxigênio singlete, indicando predominância do mecanismo tipo II.