Determination of 2,4-D and dicamba in food crops by MEKC

The determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice and corn was performed by a supercritical fluid extraction (SFE) method using CO2/acetone as extraction mix and an SFE apparatus developed in our laboratory. The extracts were cleaned up after extraction by both liquid- liquid partition and a Florisil column. Micellar electrokinetic capillary chromatography (MEKC) coupled with ultraviolet on-column detection was used for the analysis of these pesticides. The detection limits were improved by the preparation of a special detection cell with an increased pathlength that gave detection limits of ca. 0.6 pg for 2,4-D and Dicamba. Our results demonstrated that capillary electrophoresis can be a powerful new analytical tool for pesticide residue analysis.

Breve revisão de métodos de determinação de resíduos do herbicida á cido 2,4-diclorofenoxiacético (2,4-D)

This paper supplies a revision about the main techniques of extraction, clean-up and pre-concentration of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) in water and soil samples, as well as chromatographic methods and immune assays for its identification and quantification.

Absorption and translocation of 2,4-D in plants of Memora peregrina

The objective of this work was to evaluate absorption and translocation of the herbicide 2,4-D in plants of Memora peregrina. The herbicide 2,4-D was used alone with the formulation DMA 806 BR and associated with the herbicide picloram in the commercial product Padron. Levels of radioactivity on the treated leaves were determined in sample obtained after washing them with methanol and chloroform at different times after the application of the radiolabelled formulation (1, 2, 4, 8, 24, and 48 h). Translocation was evaluated by cutting plants between stem and root. The parts obtained were: root, stem, leaf treated, leaves above the leaf treated, leaves below the leaf treated, and leaf opposite of the leaf treated. These parts were weighted, dried, ground, burnt, and radioactivity in the samples was determined. The results suggest that the translocation of the radioactive herbicide 2,4-D was insignificant in plants of M. peregrina in the two treatments evaluated. Absorption of 14C 2,4-D in the treatment with DMA 806 BR and the mixture of DMA 806 BR plus Padron had the same behavior. These observations explain the inefficient control obtained with this herbicide in plant species under study.

Advances in drug design based on the amino acid approach: Taurine analogues for the treatment of CNS diseases

Amino acids are well known to be an important class of compounds for the maintenance of body homeostasis and their deficit, even for the polar neuroactive aminoacids, can be controlled by supplementation. However, for the amino acid taurine (2-aminoethanesulfonic acid) this is not true. Due its special physicochemical properties, taurine is unable to cross the blood-brain barrier. In addition of injured taurine transport systems under pathological conditions, CNS supplementation of taurine is almost null. Taurine is a potent antioxidant and anti-inflammatory semi-essential amino acid extensively involved in neurological activities, acting as neurotrophic factor, binding to GABA A/glycine receptors and blocking the excitotoxicity glutamate-induced pathway leading to be a neuroprotective effect and neuromodulation. Taurine deficits have been implicated in several CNS diseases, such as Alzheimer's, Parkinson's, epilepsy and in the damage of retinal neurons. This review describes the CNS physiological functions of taurine and the development of new derivatives based on its structure useful in CNS disease treatment.&; 2012 by the authors; licensee MDPI, Basel, Switzerland.

A new palladium chelate compound for determination of sulfide

A new palladium chelate compound is described for the determination of sulfide in aqueous samples. The reagent, bis(2-aminobenzoate)palladium(II) (PdA 2), was prepared by reaction of tetrachloropalladate (PdCl 4 -) with 2-aminobenzoic acid. The compound was characterized by infrared spectroscopy and CHN elemental analysis. The measurement was based on the selective reaction of PdA 2 with sulfide in an aqueous medium, which quantitatively produced fluorescent 2-aminobenzoate (λ ex=245nm, λ em=410nm). The analytical response was linear in the range 0.10-20.0μmol (S 2-) L -1 (r>0.99), with a limit of detection of 0.075μmolL -1 and repeatability (RSD) of 3.4%. There was no interference from CO 3 2-, NO 3 -, Cl -, SO 4 2-, Br -, NO 2 -, K +, NH 4 +, Na +, citrate or S 2O 8 2-. The fluorescence intensity decreased in the presence of H 3CCOO -, PO 4 3- and SCN -, while OH - caused a positive interference. The new fluorescent compound was successfully applied for the determination of sulfide in synthetic wastewater and natural water sample. The advantages of the proposed palladium chelate are absence of toxic by-products, simple synthesis procedure of reagent and yield reaction of about 85%, easy handling and fast acquirement of analytical signal. © 2012 Elsevier B.V.

Biomimetic sensor based on 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin iron (III) chloride and MWCNT for selective detection of 2,4-D

Exploitation of the electronic properties of carbon nanotubes for the development of voltammetric and amperometric sensors to monitor analytes of environmental relevance has increased in recent years. This work reports the development of a biomimetic sensor based on a carbon paste modified with 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H-porphyrin iron (III) chloride (a biomimetic catalyst of the P450 enzyme) and multi-wall carbon nanotubes (MWCNT), for the sensitive and selective detection of the herbicide 2,4- dichlorophenoxyacetic acid (2,4-D). The sensor was evaluated using cyclic voltammetry and amperometry, for electrochemical characterization and quantification purposes, respectively. Amperometric analyses were carried out at -100 mV vs. Ag/AgCl(KClsat), using a 0.1 mol L-1 phosphate buffer solution at pH 6.0 as the support electrolyte. Under these optimized analytical conditions, the sensor showed a linear response between 9.9 × 10-6 and 1.4 × 10-4 mol L-1, a sensitivity of 1.8 × 104 (±429) μA L mol -1, and limits of detection and quantification of 2.1 × 10 -6 and 6.8 × 10-6 mol L-1, respectively. The incorporation of functionalized MWCNT in the carbon paste resulted in a 10-fold increase in the response, compared to that of the biomimetic sensor without MWCNT. In addition, the low applied potential (-100 mV) used to obtain high sensitivity also contributed to the excellent selectivity of the proposed sensor. The viability of the application of this sensor for analysis of soil samples was confirmed by satisfactory recovery values, with a mean of 96% and RSD of 2.1% (n = 3). © 2013 Elsevier B.V.

Identificação de microrganismos resistentes ao herbicida ácido 2,4-diclorofenóxiacético (2,4-D) em solos de Rondônia, Brasil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Investigação da toxicidade e da capacidade de recuperação do herbicida 2,4-D comercial (2,4-diclorofenoxiacético) empregando brânquias de tilápias, Oreochromis niloticus, como biomarcador

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigação da toxicidade, citotoxicidade e genotoxicidade de uma formulação comercial de 2,4-D (Diclorofenoxiacético) utilizando os organismos testes Allium cepa e Tradescantia pallida

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise histopatológica de fígado de tilápias (Oreochromis Niloticus) expostas ao herbicida 2,4-D comercial

The action of man has led, over the years, major impacts on the environment, especially in aquatic ecosystems, leading to an impairment of water quality, considered one of the essential factors for the maintenance of vital functions and consequently the life of the planet. Among the activities considered a risk for the environment are linked to pollution from many sources and even entire watersheds, whether by industrial waste, sewage, or for substances used in agriculture, such as pesticides, herbicides and fertilizers. The (2,4-D) 2,4- dichlorophenoxyacetic acid is used worldwide, and the fact that its genotoxicity is proven by several studies and by its long persistence in soil, which enables the leaching and percolation of compounds affecting water bodies, toxicity studies are relevant and justifiable. Thus, this study aimed to evaluate the toxicity of 2,4-D by examining the liver of the fish Oreochromis niloticus exposed to different dilutions. Portions of liver were collected and fixed for histological and histochemical techniques to detect total proteins, polysaccharides and lipids. lipids. Treatment with 2,4-D herbicide apparently did not alter the lipid profiles, the accumulation of polysaccharides, and the presence of total proteins. The 2.5 and 5.0% were lethal to fish. These mortalities are probably of high toxic and cytotoxic potential of 2,4-D herbicide results. Several histopathological changes were found, such as: loss of cytoplasmic integrity, loss of cell limit, nuclear deformation, vacuolated cytoplasm, tissue disorganization and hydropic degeneration. Statistically significant changes were: hydropic degeneration and vacuolated cytoplasm. It is concluded, therefore, that the qualitative morphological analysis is an important method for observing changes in liver toxicology studies. As the O. niloticus species is an efficient biological indicator of water pollution by 2,4-D

Análise histopatológica de fígado de tilápias (Oreochromis Niloticus) expostas ao herbicida 2,4-D comercial

The action of man has led, over the years, major impacts on the environment, especially in aquatic ecosystems, leading to an impairment of water quality, considered one of the essential factors for the maintenance of vital functions and consequently the life of the planet. Among the activities considered a risk for the environment are linked to pollution from many sources and even entire watersheds, whether by industrial waste, sewage, or for substances used in agriculture, such as pesticides, herbicides and fertilizers. The (2,4-D) 2,4- dichlorophenoxyacetic acid is used worldwide, and the fact that its genotoxicity is proven by several studies and by its long persistence in soil, which enables the leaching and percolation of compounds affecting water bodies, toxicity studies are relevant and justifiable. Thus, this study aimed to evaluate the toxicity of 2,4-D by examining the liver of the fish Oreochromis niloticus exposed to different dilutions. Portions of liver were collected and fixed for histological and histochemical techniques to detect total proteins, polysaccharides and lipids. lipids. Treatment with 2,4-D herbicide apparently did not alter the lipid profiles, the accumulation of polysaccharides, and the presence of total proteins. The 2.5 and 5.0% were lethal to fish. These mortalities are probably of high toxic and cytotoxic potential of 2,4-D herbicide results. Several histopathological changes were found, such as: loss of cytoplasmic integrity, loss of cell limit, nuclear deformation, vacuolated cytoplasm, tissue disorganization and hydropic degeneration. Statistically significant changes were: hydropic degeneration and vacuolated cytoplasm. It is concluded, therefore, that the qualitative morphological analysis is an important method for observing changes in liver toxicology studies. As the O. niloticus species is an efficient biological indicator of water pollution by 2,4-D

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2.4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe2+ ([Fe2+](0)) from 1.0 up to 2.5 mM, the rate in mmol of H2O2 fed into the system (F-H2O2,F-in) from 3.67 up to 7.33 mmol of H2O2/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes. (C) 2012 Elsevier Ltd. All rights reserved.

End-to-end Distance Distribution in Fluorescent Derivatives of Bradykinin in Interaction with Lipid Vesicles

Cellular membranes have relevant roles in processes related to proteases like human kallikreins and cathepsins. As enzyme and substrate may interact with cell membranes and associated co-factors, it is important to take into account the behavior of peptide substrates in the lipid environment. In this paper we report an study based on energy transfer in two bradykinin derived peptides labeled with the donor-acceptor pair Abz/Eddnp (ortho-aminobenzoic acid/N-[2,4-dinitrophenyl]-ethylenediamine). Time-resolved fluorescence experiments were performed in phosphate buffer and in the presence of large unilamelar vesicles of phospholipids, and of micelles of sodium dodecyl sulphate (SDS). The decay kinetics were analyzed using the program CONTIN to obtain end-to-end distance distribution functions f(r). Despite of the large difference in the number of residues the end-to-end distance of the longer peptide (9 amino acid residues) is only 20 % larger than the values obtained for the shorter peptide (5 amino acid residues). The proline residue, in position 4 of the bradykinin sequence promotes a turn in the longer peptide chain, shortening its end-to-end distance. The surfactant SDS has a strong disorganizing effect, substantially broadening the distance distributions, while temperature increase has mild effects in the flexibility of the chains, causing small increase in the distribution width. The interaction with phospholipid vesicles stabilizes more compact conformations, decreasing end-to-end distances in the peptides. Anisotropy experiments showed that rotational diffusion was not severely affected by the interaction with the vesicles, suggesting a location for the peptides in the surface region of the bilayer, a result consistent with small effect of lipid phase transition on the peptides conformations.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE.

OSCILLATORY DYNAMICS IN SYSTEMS CONTAINING BROMATE AND 1,4-CYCLOHEXANEDIONE IN ACIDIC MEDIA. I. THE EFFECT OF TEMPERATURE. We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 degrees C. Activation energies (E-a) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the E-a was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.

Dinâmica oscilatória em sistemas contendo bromato e 1,4-ciclo-hexanodiona em meio ácido: I. Efeito da temperatura

We present in this work the influence of temperature on the dynamics of homogeneous chemical systems containing bromate and 1,4-cyclohexanedione (1,4-CHD) in acidic media. In particular, the following systems were studied: bromate/1,4-CHD/acid, bromate/1,4-CHD/ferroin/acid and bromate/1,4-CHD/trisbipyridine ruthenium/acid. Investigations were carried out by means of an electrochemical probe, at five temperatures between 5 and 45 °C. Activation energies (Ea) were estimated in different ways for the pre-oscillatory and oscillatory regimes. In any case, the Ea was found to depend on the catalyst, composition and initial concentrations. In addition, it was observed that ferroin and trisbipyridine ruthenium act as catalysts only during the transition between the induction period and oscillatory regime.