Investigating a new approach for magnetic ionic liquids: Dispersive liquid-liquid microextraction coupled to pyrolysis gas-chromatography-mass spectrometry to determine flame retardants in sewage sludge samples.

This study addresses the analysis of emerging contaminants, often using chromatographic techniques coupled to mass spectrometry. However, sample preparation is often required prior to instrumental analysis, and dispersive liquid-liquid microextraction (DLLME) is a viable strategy in this context. DLLME stands out for its ability to reduce sample and solvent volumes. Notably, dispersive liquid-liquid microextraction using magnetic ionic liquids (MILs) has gained relevance due to the incorporation of paramagnetic components in the chemical structure, thereby eliminating the centrifugation step. A pyrolizer was selected in this work to introduce sample onto the GC column, since the MIL is extremely viscous and incompatible with direct introduction through an autosampler. This study is the first to report the use of a DLLME/MIL technique for sample introduction through a pyrolizer in gas chromatography coupled to mass spectrometry (GC-MS). This approach enables the MIL to be compatible with gas chromatography systems, resulting in optimized analytical and instrument performance. The analysis of polybrominated diphenyl ether flame retardants (PBDEs) was focused on the PBDE congeners 28, 47, 99, 100, and 153 in sewage sludge samples. The [P6,6,6,14+]2[MnCl42-] MIL was thoroughly characterized using UV-Vis, Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy, as well as thermal analysis. In the chromatographic method, a pyrolyzer was used in the sample introduction step (Py-GC-MS), and critical injection settings were optimized using multivariate approaches. Optimized conditions were achieved with a temperature of 220 °C, a pyrolysis time of 0.60 min, and an injection volume of 9.00 µL. DLLME optimization was performed through central compound planning (CCD), and optimized training conditions were achieved with 10.0 mg of MIL, 3.00 µL of acetonitrile (ACN) as dispersive solvent, extraction time of 60 s, and volume of a sample of 8.50 mL. Precision was observed to range from 0.11 % to 12.5 %, with limits of detection (LOD) of 44.4 µg L-1 for PBDE 28, 16.9 µg L-1 for PBDE 47 and PBDE 99, 33.0 µg L-1 for PBDE 100 and 375 µg L-1 for PBDE 153. PBDE 28 was identified and analyzed in the sludge sample at a concentration of 800 µg L-1. The use of MIL in dispersive liquid-liquid microextraction combined with pyrolysis gas chromatography-mass spectrometry enables identification and quantification of PBDEs in sewage sludge samples at concentrations down to the µg L-1 level.

Label-Free Ultrasensitive and Environment-Friendly Immunosensor Based on a Silica Optical Fiber for the Determination of Ciprofloxacin in Wastewater Samples.

Emerging contaminants, including pharmaceutical compounds, are receiving research attention as a result of their widespread presence in effluents and wastewater treatment plants (WWTPs). The antibiotic ciprofloxacin (CIP) is extensively employed to treat infections in animal and human medicine. Both CIP and its metabolites are common contaminants found in WWTPs. In this study, a label-free ultrasensitive U-bent optical fiber-based immunosensor for the determination of CIP in wastewater samples was developed using the properties of the conducting polymer polyaniline (PANI). The anti-CIP immunoglobulin G (IgG) was deposited on a silica optical fiber surface previously functionalized with PANI. Scanning electron microscopy and micro-Raman spectroscopy were used to investigate the surface of the immunosensor. The analysis of CIP in wastewater was performed without the use of an organic solvent or sample preparation steps, with only the sample dilution in saline buffer (pH = 7.4). The linear range for CIP was from 0.01 to 10,000 ng L-1. The detection limit was 3.30 × 10-3 ng L-1 and the quantification limit was 0.01 ng L-1. The immunosensor provided a high average recovery of 91% after spiking wastewater samples with CIP at a concentration of 9,100 ng L-1. The method was applied in triplicate to wastewater samples from Quebec (Canada), obtaining concentrations of 549 and 267 ng L-1. A comparison with a reference method showed no significant difference (t-test at 95% confidence). The new technique developed is selective, allowing a quantitative analysis of CIP in wastewater.

Resistant starch/pectin free-standing films reinforced with nanocellulose intended for colonic methotrexate release.

Although resistant starch/pectin (RS/P) films have previously displayed suitable properties for colon-specific drug delivery, nanocomposite films were developed aiming to enhance physicochemical, thermal, mechanical and barrier properties, as well as the low oral bioavailability of methotrexate (MTX). FEG-SEM micrographs of nanocomposite films showed different interaction patterns occurring among nanocellulose and RS/P. The nanofiller addition led to an increase in the thermal stability, probably due to its interaction with RS crystalline double helices. Results also displayed an improvement of the puncture strength, while barrier properties revealed a low water vapor permeability. Ex vivo bioadhesion test displayed the nanocomposites films to interact strongly with porcine gastrointestinal mucosa. In vitro drug release studies showed that the films developed enhanced the drug dissolution rates with approximately 80% of MTX release in 150min, suggesting the potential of these materials as a poor solubility drugs carrier, which constitutes an important tool for enhancing oral bioavailability.

Chemical monitoring of canola, corn, olive, soybean and sunflower oils after thermal treatment at conventional temperatures in domestic stoves / Monitoramento químico dos óleos de canola, milho, oliva, soja e girassol após tratamento térmico em temperaturas alcançadas por fogões domésticos

The frying by immersion is a widely used cooking process and it improves the food texture and flavor. This study analyzed the initial thermal oxidation in five edible vegetable oils used for frying. Oils samples were heated twice for 30 minutes, at 180 C and then at 240 C simulating the domestic stoves temperatures. The oils decomposition temperatures were determined by TG, being all of them > 250 C. The FA profile was analyzed by GC-FID and a slight decrease of UFA was found in corn and soybean oils. In canola, olive and sunflower oils, UFA was stable after heating treatment. Minor FA decomposition was found in canola oil, and followed by corn, olive, sunflower and soybean oils. NIR spectroscopy analyzes resulted in an extensive bands overlapping. The spectra were modeled by PCA and the oils were classified into two groups: fresh oil and heated oil, mainly by differing in 1900 nm region, associated with the carboxyl signal decrease, which might be related to the initial FA degradation in samples. It could partially understand what occurs to the vegetable oil in the beginning of its thermo-decomposition. These information are useful to consumers, food industry and health surveillance agency.

A fritura por imersão é um processo de cocção utilizado pela inclusão de textura e sabor aos alimentos. Foi analisada a oxidação térmica inicial de cinco óleos vegetais comestíveis utilizados para fritura de imersão. Amostras de óleos foram aquecidas duas vezes por 30 minutos, a 180 ºC e depois a 240 ºC, simulando-se as temperaturas de fogões domésticos. As temperaturas de decomposição dos óleos foram determinadas por TG, sendo > 250 ºC. O perfil de FA foi analisado por GC-FID, detectando-se pequeno decréscimo dos UFA nos óleos de milho e soja. Nos óleos de canola, oliva e girassol, os UFA foram estáveis após o tratamento térmico. A menor decomposição dos FA foi detectado no óleo de canola, seguido de milho, oliva, soja e girassol. Análises por espectroscopia NIR resultaram em grande sobreposição das bandas. Os espectros foram modelados por PCA, classificando-se os óleos em dois grupos: óleo fresco e óleo aquecido, principalmente pelas diferenças na região de 1900 nm, relacionadas ao decréscimo do sinal de carboxilas, e associadas à degradação inicial dos FA nas amostras. Ainda que parcialmente, pode-se entender o que ocorre com os óleos vegetais no início de termo-decomposição, abrangências que são úteis para consumidores, indústria alimentícia e órgão de vigilância sanitária.

Chemical monitoring of canola, corn, olive, soybean and sunflower oils after thermal treatment at conventional temperatures in domestic stoves / Monitoramento químico de óleos de canola, milho, azeitona, soja e girassol após tratamento térmico a temperaturas convencionais em fogões domésticos

The frying by immersion is a widely used cooking process and it improves the food texture and flavor. This study analyzed the initial thermal oxidation in five edible vegetable oils used forfrying. Oils samples were heated twice for 30 minutes, at 180 °C and then at 240 °C simulating the domestic stoves temperatures. The oils decomposition temperatures were determined byTG, being all of them > 250 °C. The FA profile was analyzed by GC-FID and a slight decrease of UFA was found in corn and soybean oils. In canola, olive and sunflower oils, UFA was stableafter heating treatment. Minor FA decomposition was found in canola oil, and followed by corn, olive, sunflower and soybean oils. NIR spectroscopy analyzes resulted in an extensive bands overlapping. The spectra were modeled by PCA and the oils were classified into two groups: fresh oil and heated oil, mainly by differing in 1900 nm region, associated with the carboxyl signal decrease, which might be related to the initial FA degradation in samples. It could partiallyunderstand what occurs to the vegetable oil in the beginning of its thermo-decomposition. These information are useful to consumers, food industry and health surveillance agency.

A fritura por imersão é um processo de cozimento amplamente utilizado e melhora a textura e o sabor do alimento. Este estudo analisou a oxidação térmica inicial em cinco óleos vegetais comestíveis usados ​​para fritar. As amostras de óleo foram aquecidas duas vezes durante 30 minutos, a 180 ° C e depois a 240 ° C simulando as temperaturas dos fogões domésticos. As temperaturas de decomposição dos óleos foram determinadas por TG, sendo todas elas> 250 ° C. O perfil de FA foi analisado por GC-FID e uma ligeira diminuição de UFA foi encontrada em óleos de milho e de soja. Nos óleos de canola, azeite e girassol, a UFA foi estável após o tratamento térmico. A decomposição menor de FA foi encontrada em óleo de canola, seguido de óleo de milho, azeite, girassol e soja. As análises de espectroscopia NIR resultaram em uma ampla faixa de sobreposição. Os espectros foram modelados por PCA e os óleos foram classificados em dois grupos: óleo fresco e óleo aquecido, principalmente por diferença na região de 1900 nm, associado à diminuição do sinal carboxílico, o que pode estar relacionado à degradação inicial de FA nas amostras. Poderia entender parcialmente o que ocorre ao óleo vegetal no início de sua termo-decomposição. Essas informações são úteis para consumidores, indústria de alimentos e agência de vigilância da saúde.