Lung cancer is one of the main causes of death for thousands of people yearly around the world. Biomarker aldehydes, such as hexanal and heptanal, are compounds related to the development of lung cancer, which can be detected in the early stages of this disease. A methodology was proposed to determine these aldehydes in urine, with a new configuration associated with the sample preparation step. A novel strategy with a parallel-disposable pipette extraction (DPX)-cork device was used, offering a fast and affordable extraction methodology with analysis performed by high performance liquid chromatography with diode array detector. In optimization steps, multivariate and univariate designs were applied, providing the following conditions: urine sample centrifuged at 3500 rpm for 15 min, 30 µL and 6 min of dinitrophenylhydrazine impregnation, 10× urine diluted in ultrapure water, pH adjusted to 4.8, 7 extraction cycles with 1.5 min each, 30 mg of cork, 2 desorption cycles and solvent acetonitrile with 300 µL. Limits of detection were 0.13 ng mL-1 for both analytes and limits of quantification were 0.40 and 0.41 ng mL-1 for hexanal and heptanal, respectively. Intraday and interday precisions ranged from 4 to 21%. Relative recoveries ranged from 86 to 107%, assessed at three concentrations. Urine samples were analyzed, but the presence of aldehydes was not detected.

The use of extraction technique with disposable tips (DPX) was applied for the first time for the extraction and preconcentration of Yb in samples of liquid waste from the petrochemical industry and environmental water using bioabsorbent cork. The use of cork as an extracting phase in the determination of Yb by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GF AAS) was evaluated. The pyrolysis and atomization temperatures were optimized at 1400 and 2400 °C, respectively. H2SO4, HNO3 and HCl acids were compared in the steps of cleaning the extraction phase and desorption of the analyte by DPX. The best extraction in the selected conditions was obtained with pH 8.0 and 5% v/v HCl. The recoveries were close to 100% for residual water and drinking water, 33 to 77% for produced water and 64 to 93% for river water. Tests with interfering ions in different concentrations were performed. The relative limit of quantification (LOQ) and limit of detection (LOD) were estimated at 0.03 and 0.01 µg L-1, respectively. The total time for the preparation of the samples by DPX was close to 1 min per sample. Extraction and pre-concentration were observed using DPX with a pre-enrichment factor of approximately 4 times.

In this study, for the first time, histamine-functionalized magnetic nanoparticles (HIS-MNP) were used as sorbent phase combined with bar adsorptive microextraction (BAµE) for the determination of methylparaben (MP), ethylparaben (EP), propylparaben (PP), and butylparaben (BP) in water samples by high performance liquid chromatography coupled with diode array detection (HPLC-DAD). Extraction and desorption conditions, including desorption time and solvent, ionic strength effect and extraction time, were investigated. The extractions were performed for 90 min, 30% of NaCl and sample pH 5. Desorption was carried out using 250 μL of acetonitrile:methanol (25:75 v/v) for 30 min. The limits of detection (LODs) were of 1.5 μg L-1 and limits of quantification (LOQs) were 5.0 μg L-1 for all analytes. The intra-day precision ranged from 1% for EP, PP and BP to 3% for MP, EP, PP and BP. The inter-day precision ranged from 3% for EP to 18% for BP. The relative recoveries varied from 81 to 125%, and relative standard deviations (RSD) ranged between 1 and 16%.

A potential eco-friendly method without organic solvents is presented by integrating a chromatographic fingerprint and multivariate control chart based on Q residuals to differentiate grape juices from different farming practices. The sample preparation was only water dilution, and the mobile phase was water acidified with sulfuric acid, which can be readily neutralized before its disposal. The proposed method is shown to be a simple way to distinguish between organic and non-organic grape juices in a non-target way, successfully evaluating an external validation data set, where organic and non-organic samples were correctly assigned. Through the chromatographic profile, it is possible to suggest that one of the species responsible for this distinction may be from the anthocyanins class.

A simple and efficient method using reduced amounts of solvents for the determination of polycyclic aromatic sulfur heterocycles (PASHs) in aqueous matrices from a lagoon and leachate solid waste from a petrochemical industry is proposed. The target analytes were previously concentrated using the disposable pipette extraction (DPX) technique applying gas chromatography-mass spectrometry (GC-MS) for analysis. In this innovative approach, the DPX was modified with 8-hydroxyquinoline silica gel immobilized with PdII for the pre-concentration of 4-methyldibenzothiophene, 4,6-dimethyldibenzothiophene, 1,2-naphtobenzothiophene, 2-methylbenzothiophene and 3-methylbenzothiophene. To improve the extraction efficiency, parameters such as desorption solvent, ionic strength, extraction and desorption cycles were optimized. The values obtained for the limits of detection (LOD) and quantification (LOQ) are adequate for the determination of PASHs in aqueous and leachate solid waste samples. Precision and accuracy parameters showed satisfactory results, providing relative recoveries of 74.6-131.2% for PASHs from lagoon water samples and 72.7-118.0% for leachate of solid waste samples. In the lagoon samples the relative standard deviation (RSD) values for the five PASHs ranged from 0.3 to 9.2% and 3.8 to 19.4% for the leachate of the solid waste. These results demonstrate that the proposed method represents a promising alternative for the determination of PASHs in aqueous and leachate solid waste samples.

TEAM THAT GIVES ITS BEST. Football is the most practiced sport in the world, and admittedly one of the biggest cultural manifestations in Brazil. Its size and importance impact many fields of science. In this work, a playful and interactive activity is proposed, which allows the so beloved national sport and Chemistry to be united in a fun and reflective way, through the selection of the dream team. Each team can be formed by the desired tactical lineup, placing the player of your choice in the eleven available positions, describing its characteristic that makes it there. Even though it is derived from a competitive sport, there is no singular winner in this strategy, since everyone involved wins, due to the reflections and considerations developed, to the stimulus of creativity and to the fun involved in recreational activities like this.

The use of a polypyrrole (PPy) is described as an efficient extraction phase for disposable pipette extraction (DPX), in a fast and ruggedized analytical method for simultaneous determination of 18 organic micro-pollutants in water using gas chromatography-mass spectrometry (GC-MS). The DPX-blank pipettes were filled with PPy, a material produced through the chemical polymerization of PPy using iron(III) chloride hexahydrate. The optimized conditions were 5 extraction cycles with 600 µL of sample, adjusted to pH 9, and desorption with 150 µL of ethyl acetate using 7 cycles with the same aliquot. The calibration curves resulted in determination coefficient (R2) higher than 0.9963, the limit of detection (LOD) ranged from 0.4 to 1.5 µg L−1, and the limit of quantification (LOQ) were from 1.4 to 5.0 µg L−1. Excellent results were obtained for repeatability (2.3 to 15%, for 5 µg L−1) and intermediate precision, varying the day of analyses (3.9 to 15.5%) and the pipette tip (3.4 to 22.4%). The analyte recovery ranged from 75.4 to 115.0% for river water, and from 74.9 to 116.2% for tap water, in three different levels of concentration. The DPX-GC-MS method with PPy was successfully applied to determine the 18 analytes in river and tap water from the cities of Joinville and Florianópolis, Santa Catarina, Brazil.

This paper describes a new and simple electrode for the determination of bisphenol A (BPA) in different plastic samples using carbon paste electrode (CPE) modified with a trihexyltetradecylphosphonium tetrachloromanganate(II) ([P6,6,6,14+]2[MnCl42-]) magnetic ionic liquid (MIL/CPE). Electrochemical characterization of MIL/CPE by cyclic voltammetry and electrochemical impedance spectroscopy indicated that MIL facilitated the electron transfer. Using squarewave voltammetry (SWV) under optimized conditions, the calibration curve showed a linear range for BPA from 2.0 to 53.0 µmol L-1, with limit of detection (LOD) of 0.87 µmol L-1. The proposed electrode demonstrated good precision with coefficients of variation of 4.5% (intra-day, n = 10), 2.0% (inter-day, n = 5) and 1.5% (electrode-to-electrode repeatability, n = 3). Recoveries of 93.0 to 101.1% demonstrated that the method is suitable for practical applications.

In this study, a disposable pipette extraction (DPX)-based procedure was fully optimized for the multiclass determination of 12 pesticides, with significant differences in their physicochemical properties, using high-performance liquid chromatography coupled with diode array detection (HPLC-DAD). The variables optimized were type of extraction phase, sample pH, sample volume, number of extraction and desorption cycles, time of each cycle, type and volume of desorption solvent, and NaCl concentration of the samples. The analytical parameters of merit were determined under optimized conditions and satisfactory results were achieved, with limits of detection (LOQs) varying from 0.06 µg L-1 for carbofuran to 2.30 µg L-1 for carbendazim and correlation coefficients of 0.9923 to 0.9999. Relative recoveries ranged from 75 to 117%. Good results were achieved for intraday (n = 3) precision (1 to 20%) and interday (n = 9) precision (1 to 24%). The method was applied to the monitoring of 20 drinking water samples collected from water treatment plants.

In this study, the use of bracts as a natural sorbent in solid-phase microextraction was exploited for use in the determination of polycyclic aromatic hydrocarbons in water samples with separation/detection performed by gas chromatography-mass spectrometry. Fiber-to-fiber reproducibility was evaluated and the relative standard deviation (RSD) was lower than 14%. Optimizations were performed using both the proposed and DVB/Car/PDMS (divinylbenzene/carboxen/polydimethylsiloxane) fibers. The optimum extraction conditions were 80 min of extraction at 50 ºC with 12% (m/v) NaCl for the bract fiber, and 100 min of extraction at 80 ºC for the commercial fiber. The limits of detection and quantification for the proposed fiber were, respectively, 0.003 and 0.01 µg L-1 for fluorene, phenanthrene, anthracene and pyrene, and 0.03 and 0.1 µg L-1 for acenaphthylene, benzo(a)anthracene and chrysene. The method using bract fiber provided relative recoveries ranging from 68 to 117%, intraday and interday precisions lower than 17 and 19%, respectively, and extraction efficiency similar to that of the DVB/Car/PDMS fiber.

In this study, a method for the determination of 3-(4-methylbenzylidene)camphor (4-MBC) and 2-ethylhexyl 4-(dimethylamino)benzoate (OD-PABA) in river water samples employing cork as the SPME (solid-phase microextraction) fiber was developed. The extraction parameters optimized were pH, ionic strength and extraction time and temperature. For the extraction step, the sample pH was studied in univariate experiments while the extraction time, temperature and ionic strength were evaluated using a central composite design. The optimal extraction conditions were sample pH 4.0, extraction time 70 min, sample temperature 80 °C and sodium chloride concentration 6% (m v-1). The limits of quantification for 4-MBC and OD-PABA were 0.1 and 0.01 µg L-1, respectively. The linear correlation coefficients were greater than 0.97 for both analytes and the developed method showed recovery values between 67 and 107%. In an evaluation of the fiber-to-fiber reproducibility (fibers produced by different analysts), the relative standard deviation (RSD) was lower than 11% (n = 6).

Abstract This paper describes the application of the solid-phase microextraction (SPME) technique for the determination and monitoring of the volatile profile of minimally-processed pineapple fruit stored at various temperatures (-12 °C, 4 °C and 25 °C) for different periods (1, 4 and 10 days). The SPME fiber coating composed of Car/PDMS presented the best performance. The optimal extraction conditions obtained through a Doehlert design were 60 min at 35 °C. The profiles for the volatile compounds content of the fruit at each stage of storage were determined by gas chromatography-mass spectrometry (GC-MS). The variation in the volatile profile over time was greater when the fruit samples were stored at 25 °C and at -12 °C compared to 4 °C. Thus, according to the volatile profiles associated with the storage conditions evaluated in this study, packaged pineapple retains best its fresh fruit aroma when stored at 4 °C.

Microbial volatile organic compounds (MVOCs) are present in several production processes in biotechnology. In this study it is evaluated the viability of use of a method involving solid-phase microextraction (SPME), in vivo SPME, in the extraction of MVOCs, associated with the pigment production process by the Monascus fungus. PDMS/Car/DVB (50/30 µm) fiber in the headspace mode (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) were used to fermentation broth study. Seventeen compounds were found associated with the presence of the fungus, being the main ones ethanol, 2-methyl-propanol, 3-methyl-butanol, 2-methyl-butanol and 2-phenyl-ethanol. These compounds have maximum concentration of 313.87, 5.51, 2.37, 0.95 and 0.70 mg L-1. The values of biomass and red pigment found for fermentation for ten days were 4.03 ± 0.21 g L-1 and 3.96 ± 0.17 (UA480). Regular MVOC productions were observed in this study, which were useful in the prediction and control of fermentation by Monascus fungus.

<p>A new single-drop microextraction approach is proposed for the extraction of compounds with a wide range of volatilities from tap water samples with separation/detection by gas chromatographymass spectrometry. This new microextraction mode is called direct immersion-headspace-single drop microextraction (DI-HS-SDME). Trihalomethanes (THMs), hydrocarbons with low molecular weight (benzene, ethyl benzene and xylenes) and polycyclic aromatic hydrocarbons (PAHs) were the model compounds. Ten milliliters of tap water samples and drop volume of 1.5 µL of 1-octanol were used. The optimal condition for DI-HS-SDME mode was 80 min of total extraction time (48 min at 40 °C in DI-SDME mode and 32 min at 12 °C in HS-SDME mode) and the addition of 1.2 g of NaCl. The analytical figures of merit were evaluated, the limits of detection ranged from 0.03 µg L^-1 for o-xylene and ethyl benzene to 6 µg L^-1 for THMs. The proposed method represents a promising alternative for the analysis of aqueous matrices which contain compounds with very different ranges of volatility.</p>

O uso intensivo de agrotóxicos na agricultura alerta os pesquisadores a desenvolverem novos métodos de identificação destes poluentes em amostras de água. Este estudo teve como objetivo validar um método por cromatografia líquida de alta eficiência (CLAE) para determinar o agrotóxico glifosato em amostras de águas subterrâneas utilizando filtros de extração em fase sólida (SPE) após derivatização com cloroformato de 9-fluorenilmetoxicarbonil (FMOC-Cl). Para o método em CLAE, foram avaliados os principais parâmetros de validação: linearidade, especificidade, precisão, exatidão, robustez, limites de detecção e quantificação. Após validação do método foi determinada a concentração de glifosato em amostras de 13 poços tubulares profundos distribuídos na área urbana e rural no município de Chapecó, SC, Brasil. O solvente utilizado na extração do FMOC-Cl em excesso foi o diclorometano, posteriormente foi realizada filtragem em SPE C18 e injeção no cromatógrafo em coluna polimérica amino com detecção por fluorescência A curva analítica realizada em água ultrapura apresentou linearidade com coeficiente de correlação de 0,99. Os limites de quantificação e detecção foram de 0,24 e 0,07 µg L-1, respectivamente. Os testes de recuperação em águas naturais variaram de 90,37 a 101,70 %. Dos 13 poços avaliados o glifosato foi detectado em cinco, sendo que a maior concentração de glifosato encontrada foi de 6,80 µg L-1 em um poço localizado na zona rural, próximo à nascente de abastecimento do município. Apesar dos baixos níveis de glifosato detectados em nossa pesquisa, é preocupante o aparecimento destas moléculas em amostras de águas subterrâneas considerando a baixa mobilidade desta molécula no solo.

The intensive use of pesticides in agriculture has prompted researchers to develop new methods for identifying these pollutants in water. This study sought to validate a high performance liquid chromatography (HPLC) method to determine the concentration of the pesticide glyphosate in groundwater samples by using solid-phase extraction (SPE) filters after derivatization with chloroformate 9-fluorenylmethoxycarbonyl (FMOC-Cl). For the HPLC method, we evaluated the following main validation parameters: linearity, specificity, precision, accuracy, robustness, and limits of detection and quantification. After validation of the method, we determined the concentration of glyphosate in samples from thirteen deep, tubular wells distributed in urban and rural areas in Chapecó, SC, Brazil. The solvent used in the extraction of excess FMOC-Cl was dichloromethane and subsequently filtration was performed on C18 SPE, and injected into the chromatograph column in amino polymer with fluorescence detection. The analytical curve made in ultrapure water was linear, with a correlation coefficient of 0.99. The limits of detection and quantification were 0.24 and 0.07 µg L-1, respectively. Recovery tests in natural waters ranged from 90.37 to 101.70%. Glyphosate was detected in 5 of the thirteen wells evaluated. The highest concentration of glyphosate (6.80 µg L-1) was detected in a countryside well, near the municipal water supply. Despite the low levels of glyphosate detected in our study, any amount present in groundwater samples is worrisome, as these molecules have low ground mobility.