A green flow-based procedure for fluorimetric determination of acid-dissociable cyanide in natural waters exploiting multicommutation

A flow system designed with solenoid valves is proposed for determination of weak acid dissociable cyanide, based on the reaction with o-phthalaldehyde (OPA) and glycine yielding a highly fluorescent isoindole derivative. The proposed procedure minimizes the main drawbacks related to the reference batch procedure, based on reaction with barbituric acid and pyridine followed by spectrophotometric detection, i.e., use of toxic reagents, high reagent consumption and waste generation, low sampling rate, and poor sensitivity. Retention of the sample zone was exploited to increase the conversion rate of the analyte with minimized sample dispersion. Linear response (r=0.999) was observed for cyanide concentrations in the range 1-200 mu g L(-1), with a detection limit (99.7% confidence level) of 0.5 mu g L(-1)(19 nmol L(-1)). The sampling rate and coefficient of variation (n=10) were estimated as 22 measurements per hour and 1.4%, respectively. The results of determination of weak acid dissociable cyanide in natural water samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. Additionally to the improvement in the analytical features in comparison with those of the flow system with continuous reagent addition (sensitivity and sampling rate 90 and 83% higher, respectively), the consumption of OPA was 230-fold lower.

Determination of fluoroacetate and fluoride in blood serum by capillary zone electrophoresis using capacitively coupled contactless conductivity detection

Fluoroacetate is a highly toxic species naturally found in plants and in commercial products (compound 1080) for population control of several undesirable animal species. However, it is non-selective and toxic to many other animals including humans, and thus its detection is very important for forensic purposes. This paper presents a sensitive and fast method for the determination of fluoroacetate in blood serum using capillary electrophoresis with capacitively coupled contactless conductivity detection. Serum blood samples were treated with ethanol to remove proteins. The samples were analyzed in BGE containing 15 mmol/L histidine and 30 mmol/L gluconic acid (pH 3.85). The calibration curve was linear up to 75 mu mol/L (R(2) = 0.9995 for N = 12). The detection limit in the blood serum was 0.15 mg/kg, which is smaller than the lethal dose for humans and other animals. Fluoride, a metabolite of the fluoroacetate defluorination, could also be detected for levels greater than 20 mu mol/L, when polybrene was used for reversion of the EOF. CTAB and didecyldimethylammonium bromide are not useful for this task because of the severe reduction of the fluoride level. However, no interference was observed for fluoroacetate.

Electrocatalytic behavior of glassy carbon electrodes modified with multiwalled carbon nanotubes and cobalt phthalocyanine for selective analysis of dopamine in presence of ascorbic acid

This work describes the development, electrochemical characterization and utilization of a cobalt phthalocyanine modified carbon nanotube electrode for the quantitative determination of dopamine in 0.2 mol L-1 phosphate buffer contaminated with high concentration of ascorbic acid. The electrode surface was analyzed by cyclic voltammetry and electrochemical impedance spectroscopy which showed a modified surface presenting a charge transfer resistance of 500 Omega, against the 16.46 k Omega value found for the bare glassy carbon surface. A pseudo rate constant value of 5.4 x 10(-4) cm s(-1) for dopamine oxidation was calculated. Voltammetric experiments showed a shift of the peak potential of DA oxidation to less positive value at 390 mV as compared with that of a bare GC electrode at 570 mV. The electrochemical determination of dopamine, in presence of ascorbic acid in concentrations up to 0.1 mol L-1 by differential pulse voltarnmetry, yielded a detection limit as low as 2.56 x 10(-7) mol L-1.

Determination of carbaryl in tomato ""in natura"" using an amperometric biosensor based on the inhibition of acetylcholinesterase activity

This work reports the utilization of two methodologies for carbaryl determination in tomatoes. The measurements were carried out using an amperometric biosensor technique based on the inhibition of acetylcholinesterase activity due to carbaryl adsorption and a HPLC procedure. The electrochemical experiments were performed in 0.1 mol L-1 phosphate buffer solutions at pH 7.4 with an incubation time of 8 min. The analytical curve obtained in pure solutions showed excellent linearity in the 5.0 x 10(-5) to 75 x 10(-5) mol L-1 range, with the limit of detection at 0.4 x 10(-3) gL(-1). The application of such a methodology in tomato samples involved solely liquidising the samples, which were spiked with 6.0 x 10(-6) and 5.0 x 10(-5) mol L-1 carbaryl. Recovery in such samples presented values of 99.0 and 92.4%, respectively. In order to obtain a comparison, HPLC experiments were also conducted under similar conditions. However, the tomato samples have to be manipulated by an extraction procedure (MSPD), which yielded much lower recovery values (78.3 and 84.8%, respectively). On the other hand, the detection limit obtained was much lower than that for the biosensor, i.e., 3.2 x 10(-6) g L-1. Finally, the biosensor methodology was employed to analyze carbaryl directly inside the tomato, without any previous manipulation. In this case, the biosensor was immersed in the tomato pulp, which had previously been spiked with the pesticide for 8 min, removed and inserted in the electrochemical cell. A recovery of 83.4% was obtained, showing very low interference of the matrix constituents. (C) 2007 Elsevier B.V. All rights reserved.

Electroanalytical Method for the Analysis of Methyldopa In Pharmaceutical Tablets Using a Crude Extract of Laccase from Pycnoporus sanguineus as Oxidizing Agent

Several colorimetric and chromatographic methods have been used for the identification and quantification of methyldopa (MA) in pharmaceutical formulations and clinical samples. However, these methods are time- and reagent-consuming, which stimulated our efforts to develop a simple, fast, and low-cost alternative method. We carried out an electroanalytical method for the determination of MA in pharmaceutical formulations using the crude enzymatic extract of laccase from Pycnoporus sanguineus as oxidizing agent. This method is based on the biochemical oxidation of MA by laccase (LAC), both in solution, followed by electrochemical reduction on glassy carbon electrode surface. This method was employed for the determination of MA in pure and pharmaceutical formulations and compared with the results obtained using the official method. A wide linear curve from 23 x 10(-5) to 1 x 10(-4) mol L(-1) was found with a detection limit calculated from 43 x 10(-6) mol L(-1).

Caracterização hidrológica e geoquímica das áreas adjacentes aos bancos oceânicos do nordeste brasileiro

O objeto deste trabalho é fornecer dados hidrológicos com fins de caracterização e monitoramento da região da Cadeia Norte do Brasil e da Cadeia de Fernando de Noronha, assim como levantar e sistematizar informações sobre a geoquímica dos diversos tipos de sedimentos encontrados na plataforma continental externa adjacente ao banco Aracati, contribuindo para o levantamento dos potenciais sustentáveis de exploração dos recursos vivos da Zona Econômica Exclusiva. A área em estudo compreende a sub-área II, setor 1 e parte do setor 2, e está localizada entre 1oN e 5oS de latitude e entre 30o e 40oW de longitude, abrangendo uma área de aproximadamente 400.000 km2. Foram analisadas amostras coletadas em 8 estações resultando em 20 amostras de sedimentos nos anos de 1997 (verão), 1998 (outono) e 2000 (primavera) e 34 estações que originaram 272 amostras de água na primavera de 2000. As concentrações máximas dos parâmetros analisados, com exceção do fosfato, nas amostras de água se localizam na região próxima à costa. Detectou-se na área uma termoclina bem marcada, sendo mais profunda na primavera. A camada de mistura é bastante homogênea, sendo porém, mais espessa na primavera. O pH detectado encontra-se na faixa alcalina sendo os maiores valores de pH detectados na primavera. Verifica-se, um máximo de salinidade na camada de inicio da termoclina sazonal. Não verificou-se na área condição anaeróbica na coluna d’água. A distribuição de fosfato, nitrato e silicato, apresenta-se de forma muito semelhante, sendo que na primavera essas concentrações são maiores, nas camadas superficiais. Na cobertura sedimentar da plataforma continental adjacente aos bancos da cadeia norte do Brasil, encontro-se areia quartzosa, areia carbonática, fragmentos de concha, Lithothanmium e Halimedas. Os fragmentos de concha apresentaram as maiores concentrações totais de metais, enquanto Lithothanmium apresentou o maior teor de carbonato. Há uma forte correlação entre ferro e manganês na amostras de água e em todas as frações de sedimentos analisadas, sendo que nestas a relação média entre estes elementos é da ordem de 1:25. Existe forte correlação entre cromo e carbonato nas amostras que apresentam teor de carbonato maior que 20%. As amostras de areia quartzosa, fragmentos de concha e Halimedas, apresentam-se muito semelhantes quanto à distribuição de ferro, manganês, zinco e cromo. Existe forte correlação nas amostras de sedimento, assim como nas amostras de água, entre ferro, manganês, zinco, correlacionando-se também nas amostras de sedimento com o chumbo. As 8 concentrações de metais nas amostras de água apresentaram-se relativamente baixas em se comparando com as amostras de sedimento. Nas amostras de água as concentrações de cromo e chumbo estão abaixo do limite de detecção.

Detection of infectious bronchitis virus and specific anti-viral antibodies using a concanavalin A-Sandwich-ELISA

Concanavalin A-Sandwich ELISA (Con A-S-ELISA) was developed for the detection of infectious bronchitis virus (IBV) or chicken specific anti-viral antibodies. The antigen detection limit for the Con A-S-ELISA was 10(5,1) EID50/mL. Three homologous and four heterologous IBV strains were similarly detected. This assay was highly effective in detecting the virus after infected tissue homogenates were passed once in embryonated chicken eggs, showing a good agreement with virus isolation technique. The Con A-S-ELISA was also used to measure anti-IBV chicken antibodies and showed a high coefficient of correlation (r = 0.85) and an agreement of k = 0.80 with the commercially available Indirect-ELISA. The relative sensitivity and specificity between these two tests were, respectively, 92.86% and 95.65% with an accuracy of 93.39%. Thus, the Con A-S-ELISA proved to be able to detect alternatively homologous and heterologous IBV strains or specific chicken anti-IBV antibodies, using the Con A as capture reagent of this assay.

Enzymeless Hydrogen Peroxide Sensor Based on Mn-containing Conducting Metallopolymer

The [(Mn4O5)-O-IV(terpy)(4)(H2O)(2)](6+) complex, show great potential for electrode modification by electropolymerization using cyclic voltammetry. The voltammetric behavior both in and after electropolymerization process were also discussed, where the best condition of electropolymerization was observed for low scan rate and 50 potential cycles. A study in glass electrode for better characterization of polymer was also performed. Electrocatalytic process by metal centers of the conducting polymer in H2O2 presence with an increase of anodic current at 0.85 V vs. SCE can be observed. The sensor showed great response from 9.9 x 10(-5) to 6.4 x 10(-4) mol L-1 concentration range with a detection limit of 8.8 x 10(-5) mol L-1, where the electrocatalytic mechanism was based on oxidation of H2O2 to H2O with consequently reduction of Mn-IV to Mn-III. After, the Mn-III ions are oxidized electrochemically to Mn-IV ions. (C) 2012 Elsevier Ltd .... Selection and/or peer-review under responsibility of the Symposium Cracoviense Sp. z.o.o.

Adsorption and detection of DNA dendrimers at carbon electrodes

Dendritic nucleic acids are highly branched and ordered molecular structures, possessing numerous single-stranded oligonucleotide arms, which hold great promise for enhancing the sensitivity of DNA biosensors. This article evaluates the interfacial behavior and redox activity of nucleic acid dendrimers at carbon paste electrodes, in comparison to DNA. Factors influencing the adsorption behavior, including the adsorption potential and time, solution conditions, or dendrimer concentration, are explored. The strong adsorption at the anodically pretreated carbon surface is exploited for an effective preconcentration step prior to the chronopotentiometric measurement of the surface species. Coupled with the numerous guanine oxidation sites, such stripping protocol offers remarkably low detection limits (e.g., 3 pM or 2.4 femtomole of the I-layer dendrimer following a 15 min accumulation). The new observations bear important implications upon future biosensing applications of nucleic dendrimers.

Determination of fluoroacetate and fluoride in blood serum by capillary zone electrophoresis using capacitively coupled contactless conductivity detection

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

Influência espaço-temporal e fisiológica na absorção de nutrientes e elementos tóxicos por Eichhornia crassipes visando o uso adequado da sua biomassa: o caso do Rio Apodi/Mossoró - RN

This study aims to determine the amount of nutrients and toxic elements in aquatic macrophytes of species Eichhornia crassipes present in River Apodi/Mossoró - RN and check some of the possibilities of using the biomass produced, based on the influence of space - temporal and physiological absorption of nutrients by plants. For this, was determined: Leaf area, Leaf wet mass, Leaf dry mass, Real humidity, Apparent humidity, Ash, Total nitrogen, Crude protein, Calcium, Magnesium, Potassium, Total phosphorus, Sodium, Iron, Copper, Manganese, Zinc, Nickel, Cobalt, Aluminum, Cadmium, Lead and Total chromium at different times, 2 sampling points and 2 parts of plants (leaves and roots). The results show that the levels of nutrients, protein and toxic elements present in plant tissue of Eichhornia crassipes are influenced by spatial, temporal and physiological variability. In general, because the maximum values in the dry matter for total nitrogen (4.4088 g/100g), crude protein (27.5549 g/100g), total phosphorus (0.642 g/100 g), calcium (1.444 g/100g), magnesium (0.732 g/100 g), potassium (7.51 g/100 g), copper (4.4279 mg/100g), manganese (322.668 mg/100g), sodium (1.39 g/100g), iron (194.169 mg/100g) and zinc (3.5836 mg/100g), there was the possibility of using biomass of Eichhornia crassipes for various purposes such as in food animal, products production for human consumption, organic fertilizers, fabrication of brick low cost, and crafts. For all these applications requires a control of the levels of substances in plant tissue. Based on the levels of nutrients and crude protein, the younger plants (0 Month) would be best to have their biomass used. Moreover, one factor that contributes to the use of larger plants (6 Months), the levels of toxic elements which have significantly small or below the detection limit. Therefore, further studies quantifying the biomass produced/m2 at 0 and 6 months are needed for a more correct choice for the best time of harvest

Estudo integrado do potencial fitorremediador da Eichhornia crassipes em ambientes naturais e sua utilização para obtenção de extratos proteicos

This study aimed to analyze the phytoremediation potential of Eichhornia crassipes in natural environments, optimize the extraction process of crude protein from plant tissue and, obtain and characterize this process in order to determine its viability of use instead of the protein sources of animal and/or human feed. For this, it has been determined in Apodi/Mossoró river water the concentration of ammonium ions, nitrite, nitrate, calcium, magnesium, potassium, iron, copper, manganese, zinc, nickel, cobalt, sodium, aluminum, cádmium, lead, and total chromium; It was determined in plant tissue of aquatic macrophytes of Eichhornia crassipes species present in Apodi/Mossoró River the moisture content, ash, calcium, magnesium, potassium, iron, copper, manganese, zinc, nickel, cobalt, sodium, aluminum, cadmium, lead, total chromium, total nitrogen and crude protein. It was also determined the translocation factor and bioaccumulation of all the quantified elements; It was developed and optimized the extraction procedure of crude protein based on the isoelectric method and a factorial design 24 with repetition; It was extracted and characterized the extract obtained by determining the moisture content, ash, magnesium, potassium, iron, copper, manganese, zinc, nickel, cobalt, sodium, cadmium, total nitrogen and crude protein. And finally, it was also characterized the protein extract using Thermogravimetric Analysis (TG), Derived Thermogravimetric (DTG), Differential Scanning Calorimetry (DSC), Infrared Spectroscopy (FT-IR) and jelly-like electrophoresis of polyacrylamide (SDS -PAGE) to assess the their molecular weights/mass. Thus, from the results obtained for the translocation and bioaccumulation factors was found that the same can be used as phytoremediation agent in natural environments of all quantified elements. It was also found that the developed method of extraction and protein precipitation was satisfactory for the purpose of the work, which gave the best conditions of extraction and precipitation of proteins as: pH extraction equal to 13.0, extraction temperature equals 60 ° C, reaction time equals to 30 minutes, and pH precipitation equals to 4.0. As for the extract obtained, the total nitrogen and crude protein were quantified higher than those found in the plant, increasing the crude protein content approximately 116.88% in relation to the quantified contente in the vegetal tissue of macrophyte. The levels of nickel and cadmium were the unique that were found below the detection limit of used the equipment. The electrophoretic analysis allowed us to observe that the protein extract obtained is composed of low polypeptide chains by the molecular and phytochelatins, with 6 and 15 kDa bands. Analysis of TG, DTG, DSC and FT-IR showed similarities in protein content of the obtained extracts based on different collection points and 9 parts of the plant under study, as well as commercial soy protein and casein. Finally, based on all these findings, it was concluded that the obtained extract in this work can be used instead of the protein sources of animal feed should, before that, test its digestibility. As human supplementation, it is necessary to conduct more tests associated with the optimization process in the sense of removing undesirable components and constant monitoring of the water body and the raw material used

Visual detection of turkey coronavirus RNA in tissues and feces by reverse-transcription loop-mediated isothermal amplification (RT-LAMP) with hydroxynaphthol blue dye

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

Low-frequency absorption cross section of the electromagnetic waves for extreme Reissner-Nordstrom black holes in higher dimensions

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

Colorimetric enzymatic assay of L-malic acid using dehydrogenase from baker's yeast

A colorimetric method has been developed and optimized to measure L-malic acid in samples of fruit juices and wine. This method is based on oxidation of the analyte, catalyzed by malate dehydrogenase (MDH) from dry baker's yeast, and in combination with the reduction of a tetrazolium salt (MTT: 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide). In the present study, the method exhibited sensitivity in the range of 500-4000 mu M of L-malic acid in the reaction cuvette, with the lower detection limit of 6.7-10(-2) g/L, the upper limit of 53.6.10(-2) g/L and a maximum standard deviation of only 2.5 % for the analyzed samples. The MDH activity from baker's yeast was also optimized, the enzyme showed a high stability at pH=8.0-9.0 and the activity was maintained completely at temperatures up to 40 degrees C for 1 hour. The results show that the colorimetric method using enzymatic preparations from dry baker's yeast is a simple and low-cost method with possibility of wide application.