Análise de agrotóxicos em água usando extração líquido-líquido com partição em baixa temperatura por cromatografia líquida de alta eficiência

This study optimized and validated the liquid-liquid extraction technique with partition at low temperature (LLE-PLT) for identification and quantification of four pesticides (chlorpyrifos, λ-cyhalothrin, permethrin, bifenthrin) in water samples. Analyses were performed by HPLC-UV. The technique was efficient for pesticide recovery with extraction exceeding 86%. Chromatographic response was linear for the four compounds in the 10-45 µg L-1 range, with correlation coefficients greater than 0.99. Limits of detection and quantitation were less than 3.5 µg L-1 and equal to 10 µg L-1, respectively. The proposed method was applied to 29 water samples from the Jaíba Project in northern Minas Gerais.

Desenvolvimento e validação de método espectrofotométrico para determinação de corante à base de luteína adicionado em iogurte desnatado

A simple analytical method for extraction and quantification of lutein colorant added to yogurt was developed and validated. The method allowed complete extraction of carotenoids using tetrahydrofuran in vortex, followed by centrifugation, partition to diethyl ether/petroleum ether, and drying. The carotenoids dissolved in ethanol were quantified by UV-Vis spectrophotometry. This method showed linearity in the range tested (1.41-13.42 µg g-1), limits of detection and quantification of 0.42 and 1.28 µg g-1, respectively, low relative standard deviation (3.4%) and recovery ranging from 95 to 103%. The method proved reliable for quantification of lutein added to yogurt.

Chemical constituents of methanolic extracts of Jatropha curcas L and effects on Spodoptera frugiperda (J. E. Smith) (Lepidoptera: Noctuidae)

The biological activity of seven extracts from leaves of different Jatropha curcas L (Euphorbiaceae) accessions was evaluated on Spodoptera frugiperda. Methanol extracts were incorporated into an artificial diet and offered to the larval stage of S. frugiperda. The parameters evaluated were length of larval and pupal stages, mortality of larval and total cycle stage, and weight of pupae. The extracts of the EMB accessions showed the best result for larval mortality at 60.00 and 56.67%, compared with the control, respectively. Hexane partition of the methanol extract of the leaves of PM-14 accessions allowed the identification of phytosterols, phytol and n-alkanols.

Isolamento e avaliação do potencial citotóxico de derivados fenólicos de Schinus terebinthifolius Raddi (Anacardiaceae)

The EtOH extract from leaves of S. terebinthifolius was subjected to partition between EtOH:H2O and hexane, CH2Cl2, and EtOAc. The phases obtained were evaluated in vitro against human tumoral cell lines and the EtOAc phase exhibited activity. Chromatographic procedures afforded gallic acid (1), methyl (2) and ethyl (3) gallates, trans-catechin (4), quercitrin (5), and afzelin (6), being the first occurrence of 1, 4 and 6 in S. terebinthifolius.In vitro cytotoxic evaluation of 1 - 6 indicated that gallic acid (1) displayed higher activity than ethyl gallate (3) against HL-60 and HeLa cells, while compounds 2, 4 - 6 were inactive.

Estudos quimiométricos da pheo formulada em pluronics®: ação fotodinâmica Sobre Artemia salina

The self-aggregation of pheophytin, a possible photosensitizer for Photodynamic Therapy, is solved by formulation in polymeric surfactant as P-123. The photosensitizer incorporation was found to be time dependent, exhibiting two steps: a partition at the micellar interface followed by an incorporation into the micelle core. The photodynamic efficiency of the formulation was tested by the bioassays against Artemia salina. In order to evaluate how the experimental parameters: pheophytin concentration, P-123 percentage and illumination time influenced the death of artemia, the factorial design 2³ was chosen. The illumination time was found to be the main factor contributing to the mortality of artemia.

Desenvolvimento e validação do método QuEChERS na determinação de resíduos de medicamentos veterinários em leite e carne de búfalo

Analytical methods were developed and validated to determine residues of veterinary drugs in buffalo milk and meat, using the QuEChERS method and gas chromatography-mass spectrometry. Both milk and meat, at 2 g of sample, 4 mL of acetonitrile, 0.8 g of MgSO4 and 0.2 g of NaCl, were used in the liquid-liquid partition, whereas 50 mg of C18, 50 mg of PSA and 150 mg of MgSO4 were employed in the dispersive solid-phase extraction (d-SPE). The methods showed sensitivity, precision and accuracy. The quantitation limits were in agreement with the maximum residue limit established by the Codex Alimentarius, FAO and WHO.

Otimização, validação e aplicação de método para determinação da concentração residual de difenoconazol em morangos após múltiplas aplicações

Difenoconazole residues in strawberry fruit cultivated in pots were estimated using the solid-liquid extraction with low temperature partition (SLE/LTP) method for sample preparation and gas chromatography with electron capture detection (GC/ECD) for analysis. The optimized method presented excellent recovery values from fortified samples and reproducibility (average recovery values ≥ 98%; CV values < 15%). Linearity of response was demonstrated (r = 0.995) with a detection limit of 9 µg kg-1. The method was successfully applied for the determination of difenoconazole residues in strawberries. Based on these results, the fungicide dissipates quickly, but the residual concentration increases after multiple applications.

Carcinogenicidade do carbendazim e seus metabólitos

The carcinogenic potential of carbendazim and its metabolites was analyzed using statistical treatment of electronic parameters obtained from DFT/ 6-311++G(d,p) and AM1 calculations. The carcinogen-DNA interaction is described in the framework of the theory of unsynchronized resonance of covalent bond as a process of electron transfer involving the HOMO and LUMO frontier orbitals. Through a Principal Component Analysis (PCA) of the electron affinity, carcinogen-DNA interaction energy, electrostatic attraction and cell membrane permeability (dipole moment m and partition coefficient LogP) evidence was obtained showing carbendazim displays carcinogenic activity. For the metabolites of carbendazim, no evidence was found in the literature of their carcinogenic activities. However, the electronic parameters for these metabolites exhibited similarity to known carcinogens, thereby showing the importance of the results obtained in this study for a policy based on the precautionary principle.

PARTIÇÃO DE PROTEÍNAS DE SORO DE LEITE EM SISTEMAS AQUOSOS BIFÁSICOS BASEADOS EM LÍQUIDOS IÔNICOS

In this work, we used an aqueous two-phase system (ATPS) consisting of the ionic liquid [C4mim][Cl] and the salt K2HPO4 to partition α-lactalbumin, β-lactoglobulin, and lactoferrin whey proteins. Extraction efficiency values above 87% indicate that the proteins primarily migrated to the ionic liquid-rich phase (top phase). Partition coefficient values ranged from 6.17 to 8.93 for a-lactalbumin, from 22.80 to 34.55 for β-lactoglobulin, and from 26.46 to 40.06 for lactoferrin. Therefore, the saline ATPS with the ionic liquid examined in this study can be considered to be a promising alternative for extracting whey proteins.

Thermodynamic quantities of solvation and dilution for some acetanilide derivatives in octanol and water mutually saturateds

Based on published thermodynamic quantities for solution, partitioning and sublimation of acetanilide (ACN), acetaminophen (ACP) and Phenacetin (PNC), the thermodynamic quantities for drugs solvation in octanol-saturated water (W(ROH)) and water-saturated octanol (ROH(W)) as well as the drugs dilution in ROH(W) were calculated. The Gibbs energies of solvation were favourable in all cases. The respective enthalpies and entropies were negative indicating an enthalpy-driving for the solvation process in all cases. On the other hand, the Gibbs energies of dilution were favourable for ACP and PNC but unfavourable for ACN, whereas the respective enthalpies and entropies were negative for ACP and PNC but positive for ACN indicating enthalpy-driving for the dilution process in the case of the former drugs and entropy-driving for the latter. From the obtained values for the transfer processes, an interpretation based on solute-solvent interactions was developed.

Rainfall effect on dissipation and movement of diuron and simazine in a vineyard soil

From 2003 to 2007, a field study was performed in a vineyard in Chile to investigate diuron and simazine soil behavior and the effect of additional rainfall. Both herbicides were applied once a year at a rate of 2.0 kg ha-1 a.i. Herbicide concentrations in soil were measured at 0, 10, 20, 40, 90 and 340 days after application, under two pluviometric conditions, natural rainfall and natural rainfall plus irrigation with 180 mm of simulated rainfall during the first 90 days after application. Soil partition coefficient (Kd) varied in the soil profile (0 to 90 cm deep) from 6.75 to 2.04 mL g-1 and from 1.4 to 0.66 mL g-1 and the maximum soil adsorption capacity was approximately 18.3 mg g-1 and 8.3 mg g-1 for diuron and simazine, respectively. Diuron and simazine reached up to 90 and 120 cm of soil depth, with an average of 8.3% and 62.4% of herbicide moved below 15 cm in the soil, respectively. Simazine soil half-life (DT50) was 38.1 days and 7.5 days, whereas the half life for diuron varied from 68.0 and 24.6 for natural rainfall and irrigated, respectively. The average of residual simazine remaining in the whole soil profile after 90 DAA was 25.4% and 39.9% for diuron, with no effect of additional rainfall amount. At 340 DAA the amount of simazine in the whole soil profile corresponded to 13.2% of the initial amount applied, being diuron more persistent with 21.5% of the initial herbicide applied. The high movement in soil of both herbicides could be due to a non-equilibrium sorption process explained by preferential flow, low Kd and high desorption.

Climate, soil and tree flora relationships in forests in the state of São Paulo, southeastern Brasil

ABSTRACT - (Climate, soil and tree flora relationships in forests in the state of São Paulo, southteastern Brasil). With the aim of verifying possible influences of abiotic features on the spatial distribution of forest tree species and families, thirteen surveys in the state of São Paulo were selected, representing different conditions (localization at the extreme coordenates and altitudes, succesional stages, surveying methods). By applying Jaccard's Index to the binary matrices of 806 synonymized specific binomina and 79 families (Cronquist's system) phenograms were constructed using the method of the unweighted pair grouping by mathematical average (UPGMA). The species formed two floristic blocks: hygrophyllous (yearly rainfall greater than 2000 mm without dry season) and mesophyllous (yearly rainfall about 1400 mm with variable dry season). The latter was divided in two other groups: the high-altitudinal (median altitudes higher than 750 m, frost average frequency greater than 3 days/year) and low-altitudinal. Both mesophyllous floristic blocks were subdivided according to soil conditions (texture, eutrophism, acid or allic dystrophism, iron content). At the family level the relations were weak, but also showed the soil nutritional status as a possible constraint to the spatial partition of families.

Nuclear exclusion of transcription factors associated with apoptosis in developing nervous tissue

Programmed cell death in the form of apoptosis involves a network of metabolic events and may be triggered by a variety of stimuli in distinct cells. The nervous system contains several neuron and glial cell types, and developmental events are strongly dependent on selective cell interactions. Retinal explants have been used as a model to investigate apoptosis in nervous tissue. This preparation maintains the structural complexity and cell interactions similar to the retina in situ, and contains cells in all stages of development. We review the finding of nuclear exclusion of several transcription factors during apoptosis in retinal cells. The data reviewed in this paper suggest a link between apoptosis and a failure in the nucleo-cytoplasmic partition of transcription factors. It is argued that the nuclear exclusion of transcription factors may be an integral component of apoptosis both in the nervous system and in other types of cells and tissues.

Environmental blue light prevents stress in the fish Nile tilapia

The present study aimed to test the effects of blue, green or white light on the stress response of the Nile tilapia, Oreochromis niloticus (L.). Each color was tested on two groups of isolated adult Nile tilapia (8 replicates each): one being subjected to confinement stress, and the other not (control). A different environmental color was imposed on each compartment by covering the light source with cellophane of the respective color (green or blue; no cellophane was used for white light). The intensity of green, white and blue lights was 250, 590 and 250 lux, respectively. Basal plasma cortisol levels were determined for each fish prior to the experimental procedures. The fish were confined by being displaced toward one side of the aquarium using an opaque partition for 1 h both in the morning and the afternoon of the two consecutive days of the test. At the end of this 48-h period, plasma cortisol levels were measured again. Basal cortisol levels (ng/ml) were similar for each group (ANOVA, F(2;42) = 0.77, P = 0.47). Thus, plasma cortisol levels were analyzed in terms of variation from their respective basal level. After confinement, plasma cortisol levels were not increased in fish submitted to a blue light environment. Thus, blue light prevents the confinement-induced cortisol response, an effect not necessarily related to light intensity.