Aplicação de carepa de aço para degradação de 2,4-dinitrofenol por meio de sistema de oxidação avançada do tipo Fenton / Application of steel waste for 2.4-dinitrophenol degradation through Fenton type advanced oxidation system

RESUMO Considerado um poluente prioritário de reconhecida toxicidade e recalcitrância, o 2,4-dinitrofenol (2,4-DNF) presente em águas residuárias dificulta tratamentos convencionais, especialmente os de princípio biológico, como lagoas aeradas e sistema de lodos ativados. Em função de sua potencialidade de transformar a estrutura de poluentes em elementos de capacidade poluidora reduzida, os processos oxidativos avançados (POAs) representam atualmente uma alternativa para o tratamento de efluentes contaminados com compostos dessa natureza. A presente pesquisa teve como objetivo realizar estudos de degradação de 2,4-DNF em solução aquosa por meio de processos de oxidação avançada do tipo Fenton utilizando uma fonte não convencional de ferro na forma de um resíduo siderúrgico (carepa de aço). A condução de um delineamento experimental fundamentado em planejamento fatorial de experimentos revelou que as variáveis quantidade de peróxido de hidrogênio e de carepa influenciaram significativamente a degradação de 2,4-DNF, proporcionando, em condições otimizadas (20 g de carepa, 0,5 mL de H2O2 em pH 3), elevada eficiência na degradação tanto do composto modelo quanto de seus intermediários reacionais, tendo reduzido também a toxicidade aguda medida na forma de inibição de crescimento de E. coli. Ensaios adicionais sugeriram que os mecanismos reacionais pelos quais ocorre a degradação do 2,4-DNF são mediados tanto pela superfície das partículas de carepa quanto pelo ferro lixiviado, caracterizando o processo como uma combinação de oxidação homogênea e heterogênea. Finalmente, ensaios de reusabilidade e operação em reator de fluxo contínuo sugeriram significativa potencialidade do sistema carepa/H2O2.

ABSTRACT Considered a priority pollutant of recognized toxicity and recalcitrance, 2.4-dinitrophenol (2.4-DNP) present in wastewater hinders conventional treatments such as filtration, chemical coagulation, activated sludge system and activated carbon adsorption. Due to the potential of advanced oxidation processes (AOP) to transform the structure of pollutants into elements of reduced pollutant capacity, they presently represent an alternative for the treatment of effluents contaminated with these compounds. The present research aimed to study the degradation of 2.4-DNP in aqueous solution through advanced Fenton-type oxidation processes, using an unconventional source of iron in the form of a steel residue (steel waste). The conduction of an experimental design based on the factorial planning of experiments revealed that the variables hydrogen peroxide quantity and scale significantly influenced 2.4-DNF degradation, providing, under optimized conditions (20 g of steel waste, 0.5 mL of H2O2 at pH 3) high degradation efficiency of both the model compound and its reaction intermediates, as well as reducing acute toxicity, measured as E. coli growth inhibition. Further trials have suggested that the reaction mechanisms by which 2.4-DNF degradation occurs are mediated by both the surface of steel waste particles and the leached iron, characterizing the process as a combination of homogeneous and heterogeneous oxidation. Finally, reusability and continuous flow reactor operation tests suggested the significant potential of the steel waste/ H2O2 system.

Analysis of 2,4-Dinitrophenol in Postmortem Blood and Urine by Gas Chromatography-Mass Spectrometry: Method Development and Validation and Report of Three Fatalities in the United States.

2,4-dinitrophenol (2,4-DNP) is a compound used in the early 1900s as a weight-loss drug but later prohibited due to its severe adverse effects, including death. It has however been attracting interest, due to its weight-loss properties, and appears to be re-emerging in forensic casework. As 2,4-DNP is available for use in industry and as a pesticide and easily accessible online, the dissemination of this drug can be fast. The compound exerts its effects through inhibition of ATP synthesis, and corresponding thermogenic energy loss which can be fatal. A method for qualitative and quantitative analysis of 2,4-DNP in blood and urine specimens using GC-MS with hydrogen as carrier gas is described. The method was validated and displayed acceptable performance parameters with linearity (R2 higher than 0.998), inter-assay imprecision (lower than 10.6%), intra-assay imprecision (lower than 10.7%), and extraction efficiency (92.1%). Stability of 2,4-DNP in blood and urine was studied, and the drug was stable up to 30 days refrigeration or frozen. Six cases in United States suspected to be related to 2,4-DNP were analyzed. Three cases were found to be positive for 2,4-DNP. Concentrations of 2,4-DNP were in the range of 61.6-220 mg/L in urine and <3-114 mg/L in blood. Based on our findings, we suggest that medical examiners and forensic toxicologists be aware of the reappearance of 2,4-DNP, including this compound as a target in death investigations related to weight-loss drugs.

Energy Metabolism and Redox State in Brains of Wistar Audiogenic Rats, a Genetic Model of Epilepsy.

The Wistar Audiogenic Rat (WAR) strain is a genetic model of epilepsy, specifically brainstem-dependent tonic-clonic seizures, triggered by acute auditory stimulation. Chronic audiogenic seizures (audiogenic kindling) mimic temporal lobe epilepsy, with significant participation of the hippocampus, amygdala, and cortex. The objective of the present study was to characterize the mitochondrial energy metabolism in hippocampus and cortex of WAR and verify its relationship with seizure severity. Hippocampus of WAR naïve (no seizures) presented higher oxygen consumption in respiratory states related to the maximum capacities of phosphorylation and electron transfer system, elevated mitochondrial density, lower GSH/GSSG and catalase activity, and higher protein carbonyl and lactate contents, compared with their Wistar counterparts. Audiogenic kindling had no adding functional effect in WAR, but in Wistar, it induced the same alterations observed in the audiogenic strain. In the cortex, WAR naïve presented elevated mitochondrial density, lower GSH/GSSG and catalase activity, and higher protein carbonyl levels. Chronic acoustic stimulation in Wistar induced the same alterations in cortex and hippocampus. Mainly in the hippocampus, WAR naïve presented elevated mRNA expression of glucose, lactate and excitatory amino acids transporters, several glycolytic enzymes, lactate dehydrogenase, and Na+/K+ ATPase in neurons and in astrocytes. In vivo treatment with mitochondrial uncoupler 2,4-dinitrophenol (DNP) or N-acetylcysteine (NAC) in WAR had no effect on mitochondrial metabolism, but lowered oxidative stress. Unlike DNP, NAC downregulated all enzyme genes involved in glucose and lactate uptake, and metabolism in neurons and astrocytes. Additionally, it was able to reduce brainstem seizure severity in WAR. In conclusion, in WAR naïve animals, both cerebral cortex and hippocampus display elevated mitochondrial density and/or activity associated with oxidative damage, glucose and lactate metabolism pathways upregulation, and increased Na+/K+ ATPase mRNA expression. Only in vivo treatment with NAC was able to reduce seizure severity of kindled WARs, possibly via down regulation of glucose/lactate metabolism. Taken together, our results are a clear contribution to the field of mitochondrial metabolism associated to epileptic seizures.

Degradation of 1-hydroxy-2,4-dinitrobenzene from aqueous solutions by electrochemical oxidation: role of anodic material.

Electrochemical oxidation (ECOx) of 1-hydroxy-2,4-dinitrobenzene (or 2,4-dinitrophenol: 2,4-DNP) in aqueous solutions by electrolysis under galvanostatic control was studied at Pb/PbO2, Ti/SnO2, Ti/IrxRuySnO2 and Si/BDD anodes as a function of current density applied. Oxidative degradation of 2,4-DNP has clearly shown that electrode material and the current density applied were important parameters to optimize the oxidation process. It was observed that 2,4-DNP was oxidized at few substrates to CO2 with different results, obtaining good removal efficiencies at Pb/PbO2, Ti/SnO2 and Si/BDD anodes. Trends in degradation way depend on the production of hydroxyl radicals (OH) on these anodic materials, as confirmed in this study. Furthermore, HPLC results suggested that two kinds of intermediates were generated, polyhydroxylated intermediates and carboxylic acids. The formation of these polyhydroxylated intermediates seems to be associated with the denitration step and substitution by OH radicals on aromatic rings, this being the first proposed step in the reaction mechanism. These compounds were successively oxidized, followed by the opening of aromatic rings and the formation of a series of carboxylic acids which were at the end oxidized into CO2 and H2O. On the basis of these information, a reaction scheme was proposed for each type of anode used for 2,4-D oxidation.

Determinación d la cinética de adsorción de 2,-dinitrofenol en carbonizado dee hueso bovino por espectrofotometríauvv-vis / Deterination of the 2,4-dinitrofenoladsorption kinetic on bovine boone char by uv-vis spectrophotometry / Determinação a ccinética de adsorção de 2,4-dnitrofenol em carbonizado de ossso bovino por espectrofotometría uv-iss

Se obtuvo un material adsorbente mediante tratamiento térmico de hueso bovino. Este carbonizado presenta un área superficial de 171 m²g-1, características texturales de un material mesoporoso y presencia del componente principal de la matriz ósea: hidroxiapatita. Se llevó a cabo la adsorción de 2,4-di-nitrofenol sobre el carbonizado en solución acuosa, en función del tiempo, y se determinó la cinética de adsorción por los modelos de seudo primer y seudo segundo orden. Además, se identificó el mecanismo de difusión mediante el modelo de difusión intrapartícula. Se observa que los datos cinéticos experimentales tienen mayor correlación con el modelo de seudo segundo orden. El modelo de difusión intrapartícula muestra que el proceso de adsorción está gobernado por la etapa en donde el mecanismo de difusión de partícula es la limitante de la velocidad.

Adsorbent material was obtained by heat treatment of bovine bone. This char has a surface area of 171 m²g-1, textural characteristics of a mesoporous material, and presence of the principal component of bone matrix-hidroxiapatite. The 2,4-dinitrophenol adsorption from aqueous solution in function of time was carried on the charred and determined the kinetics of adsorption by models of pseudo-first and pseudo second order. Additionally, we identified the diffusion mechanism through intraparticle diffusion model. The experimental kinetic data are more correlated with the pseudo second order model. The intraparticle diffusion model shows that the adsorption process is governed by stage where the diffusion particle mechanism is the rate-limiting.

Se obteve um material adsorbente mediante tratamento térmico de osso bovino. Este carbonizado apresenta um área superficial de 171 m²g-1, características texturais de um material mesoporoso e presença do componente principal da matriz óssea: hidroxiapatita. A adsorção de 2,4-dinitrofenol desde solução acuosa, em função do tempo, se levou a cabo sobre o carbonizado e se determinou a cinética de adsorção pelos modelos de seudo primeiro e seudo segundo ordem. Além disso, identifica-se o mecanismo de difusão mediante o modelo de difusão intrapartícula. Se observa que os dados cinéticos experimentais têm maior correlação com o modelo de seudo segundo ordem. O modelo de difusão intrapartícula mostra que o processo de adsorção está governado pela etapa onde o mecanismo de difusão de partícula é a limitante da velocidade.

Neuroprotective actions of 2,4-dinitrophenol: Friend or foe?

2,4-dinitrophenol (DNP) has long been known to be toxic at high concentrations, an effect related to uncoupling of mitochondrial oxidative phosphorylation. Five years ago, however, we reported that low concentrations of DNP protect neurons against the toxicity of the amyloid-ß peptide. Since then, a number of other studies have provided evidence of beneficial actions of DNP (at low concentrations), including neuroprotection against different types of insult, blockade of amyloid aggregation, stimulation of neurite outgrowth and neuronal differentiation, and even extension of lifespan in certain organisms. Some of these effects appear due to mild mitochondrial uncoupling and prevention of oxidative stress, whereas other actions are related to activation of additional intracellular signaling pathways. This study discusses the evidence supporting beneficial neuroprotective actions of DNP. DNP and other compounds with similar biological activities may be of interest in the development of novel therapeutic approaches for neurodegenerative diseases and other neurological disorders.

O 2,4-dinitrofenol (DNP) tem sido conhecido há bastante tempo como tóxico em altas concentrações, um efeito relacionado a desacoplamento da fosforilação oxidativa nas mitocôndrias. Há cinco anos, entretanto, nós relatamos que baixas concentrações do DNF protegem neurônios da toxicidade do peptídeo ß-amilóide. Desde então, outros estudos trouxeram evidência adicional dos efeitos benéficos do DNP (em baixas concentrações), incluindo neuroproteção contra diferentes tipos de agressão, bloqueio da agregação do amilóide, estimulação de crescimento neurítico e diferenciação neuronal, e mesmo extensão da sobrevida em alguns organismos. Alguns desses efeitos parecem ser devidos a leve desacoplamento mitocondrial e prevenção do estresse oxidativo, enquanto outras ações são relacionadas à ativação de sistemas adicionais de sinalização intracelular. Este estudo discute a as evidências que dão suporte a ações neuroprotetoras benéficas do DNP. DNP e outros compostos com atividades biológicas similares podem ser de interesse no desenvolvimento de novas abordagens terapêuticas para doenças neurodegenerativas e outros transtornos neurológicos.