Elisabete Alves Pereira

Estratégias de pré-concentração em eletroforese capilar (CE): parte 1. Manipulação da velocidade eletroforética do analito

Capillary electrophoresis has become a well-established and routine-based separation technique. It is based on the differences between charged analyte mobility in aqueous or organic electrolytes. Its major limitation is the sensitivity due to small sample injection volumes and the narrow diameter of the capillaries, especially when UV detection is used. There are a number of ways to increase the concentration sensitivity. This report shows some on-line preconcentration strategies to perform it in free solution capillary electrophoresis that are based on manipulation of the analyte electrophoretic velocity during the sample introduction (stacking, field amplification and transient isotachophoresis).

Derivatizing assay for the determination of aldehydes using micellar electrokinetic chromatography.

In this work, the use of a novel derivatization agent for the determination of aldehydes (in this particular case: formaldehyde, acetaldehyde, propionaldehyde, and valeraldehyde) using micellar electrokinetic chromatography is reported. The derivatization reaction is based on the reaction of aldehydes with benzhydrazide to form the corresponding derivates with maximum absorbance at 250 nm. The experimental conditions of the derivatization reaction as well of the separation were optimized. The adducts were separated with a +22 kV voltage at a temperature of 29°C. The adducts’ separation was performed in less than 14 min using as the running buffer a mixture containing 110 mmol/L of sodium dodecyl sulfate and 27 mmol/L of sodium tetraborate at pH 9.45. Samples were injected using hydrodynamic mode (50 mbar × 5 s). The calibration curves were linear up to 15.0 mg/L with r2 above 0.99. Intra and inter‐day precisions were in average 3 and 4%, respectively, and recoveries were in average of 95%. Limits of detection and quantification were around 0.5 and 1.5 mg/L, respectively. The developed method was successfully applied in the analysis of low molar weight aldehydes in yogurt and vinegar samples.

Estratégias de pré-concentração em eletroforese capilar: parte 2. Manipulação da velocidade da fase dispersa/secundária

This work describes CE preconcentration strategies based on the effect of manipulation of the disperse/secondary velocity. Introduced by Terabe et al. in 1984, micellar electrokinetic chromatography is a powerful separation approach that increases the usage of electrokinetic phenomena for the separation of nonionic compounds. The main disadvantage of MEKC is the low concentration sensitivity associated with the limited optical path length for on-capillary photometric detection and the limited volume of sample solution that can be injected. This paper compiles on-line concentration strategies for neutral analytes by sample stacking and sweeping in micellar electrokinetic chromatography.

CO2 emission from soil after reforestation and application of sewage sludge

This study aimed to quantify the carbon dioxide emissions from an Oxisol under degraded pasture located in Sorocaba, Sao Paulo State, Brazil. The treatments were: sewage sludge (LE), sewage sludge compost (CLE), mineral fertilizer (AM) and no fertilization (T0). The experiment was conducted in a completely randomized block design with analysis of the effect of the four treatments (CLE, LE, and AM T0) with four replications. The application of sewage sludge, sewage sludge compost, mineral fertilizer and no fertilizer was statistically significant for the variables of height increase and stem height of Guanandi seedlings (Calophyllum brasiliense Cambessedes - Calophyllaceae). Treatments showed significant differences in terms of CO2 emissions from soil. The CLE exhibited the highest CO2 fluxes, reaching a peak of 9.33±0.96 g C m - 2 day - 1 (p<0.0001), as well as the LE with a maximum CO2 flux of 6.35±1.17 C m - 2 day - 1 (p<0.005). The AM treatment (4.96±1.61 g C m - 2 day - 1) had the same statistical effect as T0 (5.33±0.49 g C m - 2 day - 1). CO2 fluxes were correlated with soil temperature in all treatments. However, considering the period of 172 days of evaluation, the total loss of C as CO2 was 2.7% for sewage sludge and 0.7% for the sewage sludge compost of the total C added with the application on soil.

Desenvolvimento e validação de método analítico para determinação de benzoato, sorbato, metil e propilparabenos em produtos alimentícios utilizando a eletroforese capilar

In this work, a rapid and simple method using capillary electrophoresis (CE) was developed for the determination of the benzoate, sorbate, methyl and propylparaben in foodstuffs. A running buffer consisting of 20 mmol L-1 (pH = 9.3) tetraborate enabled separation of the analytes in less than 5 min. The detector wavelength was set at 220 nm. The method was successfully applied to the analysis of sodas, sweeteners, sauces and juices. The range of preservatives found were from 478.5-466.6 mg kg-1 for methylparaben , 83.7-231.3 mg kg-1 for sorbate and 336.7-428.3 mg kg-1 for benzoate.

4-hydrazinobenzoic acid as a derivatizing agent for aldehyde analysis by HPLC-UV and CE-DAD

Aldehydes are relevant analytes in a wide range of samples, in particular, food and beverages but also body fluids. Hydrazines can undergo nucleophilic addition with aldehydes or ketones giving origin to hydrazones (a group of stable imines) that can be suitably used in the identification of aldehydes. Herein, 4-hydrazinobenzoic acid (HBA) was, for the first time, used as the derivatizing agent in analytical methodologies using liquid chromatography aiming the determination of low-molecular aldehydes. The derivatization reaction was simultaneously performed along with the extraction process, using gas-diffusion microextraction (GDME), which resulted in a clean extract containing the HBA-aldehyde derivates. The corresponding formed imines were determined by both high-performance liquid chromatography (LC) with UV spectrophotometric detection (HPLC-UV) and capillary electrophoresis with diode array detection (CE-DAD). HBA showed to be a rather advantageous derivatization reagent due to its stability, relatively high solubility in water and other solvents, high selectivity and sensibility, reduced impurities, simple preparation steps and applicability to different separation and/or different detection techniques. Limits of detections (LODs) of the optimized methodologies (in terms of time and pH among other experimental variables) were all below 0.5 mg L-1, using both instrumental techniques. Furthermore, for the first time, the HBA-aldehyde derivatives were analyzed by LC with mass spectrometry (LC-MS), demonstrating the possibility of identification by MS of each compound. The developed methodologies were also successfully applied in the analysis of formaldehyde and acetaldehyde in several alcoholic beverages. This was also the first time GDME was combined with CE, showing that it can be a valuable sample preparation tool for electrophoresis, in particular by eliminating the interference of ions and inorganic constituents present in the samples.

Methodology for soil respirometric assays: Step by step and guidelines to measure fluxes of trace gases using microcosms

Graphical abstract

Determination of glyphosate and aminomethylphosphonic acid by capillary electrophoresis with indirect detection using pyridine-2,6-dicarboxylic acid or 3,5-dinitrobenzoic acid

ABSTRACT Glyphosate (GlyP), a widely used nonselective herbicide, and aminomethylphosphonic acid (AMPA), GlyP’s most common product of degradation in the environment, seem not to pose any major health threats. However, due to their persistence and the large quantities applied worldwide, they have become a source of concern. This justifies that their simple and swift determination is of considerable relevance. This work presents two indirect capillary electrophoretic methodologies using as chromophores 3,5-dinitrobenzoic acid (DNB) and pyridine-2,6-dicarboxylic acid (PDC), both associated with hexadecyltrimethylammonium bromide (CTAB). Although both methods showed suitable analytical parameters, DNB evidenced to be slightly superior. The recoveries values were close to 100%, correlation coefficients were above 0.99 and the limits of detection (LODs) values were below 0.5 mg L−1 (2.9 µmol L−1) and 0.4 mg L−1 (3.6 µmol L−1) for GlyP and AMPA, respectively.

AVALIAÇÃO DE DIFERENTES REAGENTES COLORIMÉTRICOS PARA A DETERMINAÇÃO DE FORMALDEÍDO EM AMOSTRAS DE AR EM AMBIENTES INTERNOS

Different colorimetric reagents, the Nash reagent (acetylacetone/ammonia solution), Purpald (4-amino- 3-hydrazino-5-mercapto-1,2,4-triazole/sodium hydroxide solution) and 3-methyl-2-benzothiazolinone hydrazone (MBTH), were evaluated for the determination of formaldehyde in indoor air samples. Analytical parameters such as color stability of the product formed, sampling efficiency and reaction conditions were compared for the methodologies. Several method validation parameters were determined for the three colorimetric methods. The MBTH method showed better results and was used for the determination of formaldehydes in indoor environments.