Polyaniline-silica doped with oxalic acid as a novel extractor phase in thin film solid-phase microextraction for determination of hormones in urine.

In this study, different polyanilines were synthesized and evaluated for the determination of three hormones, including 17-ß-estradiol, 17-α-ethinylestradiol, and estrone, in urine using a novel methodology based on thin film solid-phase microextraction technique, employing the sampling well plate system. The extractor phases, designated as polyaniline doped with hydrochloric acid, polyaniline doped with oxalic acid, polyaniline-silica doped with hydrochloric acid, and polyaniline-silica doped with oxalic acid, were characterized by electrical conductivity measurements, scanning electron microscopy, and Fourier transform infrared spectroscopy. The optimized extraction conditions were composed of 1.5 mL of urine and pH adjusted to 10, with no need to dilute sample and the desorption step, 300 µL of acetonitrile was used. The calibration curves were performed in the sample matrix, with detection and quantification limits ranged from 0.30 to 3.03 µg L-1 and from 1.0 to 10.0 µg L-1 , respectively, with r ≥ 0.9969. The relative recoveries ranged from 71% to 115%, and intraday precision showed values ≤12% and interday ≤20%. The applicability of the method was successfully evaluated, and six urine samples from female volunteers were analyzed. The analytes were not detected or were below the limits of quantification in these samples.

Magnetic restricted-access carbon nanotubes for SPME to determine cannabinoids in plasma samples by UHPLC-MS/MS.

This manuscript describes the development of magnetic restricted-access carbon nanotubes (M-RACNTs) for use as SPME sorbent to determine cannabidiol (CBD) and delta-9-tetrahydrocannabinol (THC) in human plasma samples by UHPLC-MS/MS. The adsorptive phase was immobilized on an SPME device by electromagnetic interactions between the M-RACNTs and a cylindrical neodymium magnet (3-mm diameter x 8-mm height) attached to a stainless-steel rod (3-mm diameter x 40-mm height). The M-RACNTs were synthesized by incorporating Fe3O4 magnetic nanoparticles (MNPs) into commercial carbon nanotubes (CNTs); then the surface of the resulting sorbent was further coated with a layer of bovine serum albumin (BSA). Characterization techniques (SEM, FTIR, and Zeta potential) confirmed the presence of both MNPs and BSA layer dispersed through the structure of the CNTs. The M-RACNTs presented adequate sorption capacity, stable physical/chemical characteristics, and appropriate magnetic properties. Protein exclusion capacity (about 98.5%) was attributed to the chemical diffusion barrier created by the BSA network at the outer surface of the sorbent. The SPME parameters (sample pH, equilibrium time, and desorption conditions) were optimized by design of experiments (fraction factorial planning). The method (validated according to the FDA guidelines) presented adequate selectivity and linearity (coefficient of determination higher than 0.99) at concentrations ranging from the lower limit of quantification (LLOQ) (10 ng mL-1) to the upper limit of quantification (ULOQ) (300 ng mL-1) for both CBD and THC. Precision and accuracy varied from 4.47 to 19.84% (LLOQ) and -6.90 to 17.78% (LLOQ), respectively. Carry-over and matrix effect were not significant. The method was successfully applied to determine plasmatic CBD levels in healthy volunteers attending a single session of oral drug administration and THC levels in frequent cannabis smokers.

Determination of hormones in urine by hollow fiber microporous membrane liquid-liquid extraction associated with 96-well plate system and HPLC-FLD detection.

In this work, hollow-fiber microporous membrane liquid-liquid extraction (HF-MMLLE) was associated with a 96-well plate system for the determination of estrone, 17-ß-estradiol, estriol and 17-α-ethinylestradiol in urine samples. This method exhibited some advantages, such as low cost, easy application, high-throughput and environmentally-friendly aspects. The type of organic solvent to fill the membrane, ionic strength effect, sample dilution, extraction and desorption time, and desorption solvent were examined. After the optimizations, the conditions were comprised of 45 min of extraction, 1-octanol as organic solvent and 15% (w/v) of NaCl; methanol was used as desorption solvent, and the desorption time was fixed at 10 min. The dilution of the sample increased the sensitivity due to the reduction of matrix effects; thus, urine samples were diluted 40-fold. The limits of detection ranged from 0.03 µg L-1 for 17-ß-estradiol to 15 µg L-1 for estrone, and the limits of quantification ranged from 0.1 µg L-1 for 17-ß-estradiol to 10 µg L-1 for estrone. The intra-day precision varied from 1.0% for estriol to 13.3% for 17-α-ethinylestradiol, and inter-day precision varied from 7.3% for estrone to 18.1% for estriol. The relative recoveries varied from 82 to 118%.

Multiclass determination of endocrine disruptors in urine by hollow fiber microporous membrane and liquid chromatography.

A simple and rapid methodology was developed using hollow fiber membrane microporous and a 96-well plate system for a high throughput multiclass determination of endocrine disruptors in human urine (diclofenac, diazepam, carbamazepine, ibuprofen, naproxen, carbofuran, methyl parathion, 17-α-ethynyl estradiol, bisphenol A and benzophenone). The quantification and detection of the chemicals were carried out by an HPLC-diode array detector. The fixed conditions for carrying out the method optimization were 1.5 mL of sample and 300 µL of solvent desorption. Multivariate and univariate models were applied to optimize the parameters of the method, achieving the following conditions: 20% diluted urine, 1-octanol of extraction solvent impregnated in the microporous membrane, 70 min extraction in pH 3.0 and 30 min with a mixture of 75% methanol and 25% acetonitrile (v/v) for the desorption. The R2 were ≤ 0.9973 for ibuprofen. The LOD ranged from 3.3 to 16.7 ng mL-1 and the LOQ from 10 to 50 ng mL-1. Relative recoveries ranged from 71% to 126%. The repeatability (n = 3) ranged from 0.22% to 12.01%, and the intermediate precision (n = 9) ranged from 0.13% to 17.76%. The method presents a good alternative for the determination of different classes of compounds in human urine.

Disposable pipette extraction: A critical review of concepts, applications, and directions.

Analytical chemistry has always been evolving towards techniques that are increasingly simple and effective and that conform to green principles. Disposable pipette extraction (DPX, also known as dispersive pipette tip solid phase extraction) is a recent technique that has become an interesting tool in sample preparation methodologies. The principle is based on a dynamic mixture between the matrix and the sorbent which allows rapid and effective extraction of analytes and provides vigorous clean-up of the samples. In the context of fitting in with green chemistry, DPX has contributed to replacing commercially available materials with natural alternative materials. The production of these materials is also simple, reduces sample/solvent volumes, consequently generates less waste and is less laborious and safer for the laboratory worker. This review is a source of information about the DPX technique, dealing with its basic concepts, procedure, optimizations, materials for the main applications published so far, which are in the food, environmental and biological (forensic) sciences.

Exploring the use of cork pellets in bar adsorptive microextraction for the determination of organochloride pesticides in water samples with gas chromatography/electron capture detection quantification.

In this study, a biosorbent material with characteristics for the adsorption of organic compounds was used for a cork pellet-based bar adsorptive microextraction technique, as a new greener alternative for the determination of organochlorine compounds. Aldrin, chlordane, dieldrin, endrin, lindane, 4,4-DDD, 4,4-DDE, 4,4-DDT, α-endosulfan and ß-endosulfan were analyzed in water samples (drinking water, stream water and river water) with separation/detection by gas chromatography and electron capture detection (GC/ECD). The parameters that can affect the sample preparation efficiency such as desorption solvent and time as well as extraction time and ionic strength were evaluated by multivariate and univariate designs. Cork pellets (10  ×  Ø 3 mm) were used for the extraction of 15 mL of sample in the optimal conditions: 60 min of agitation with no salt added to the sample, followed by desorption of the cork pellet with 120 µL of ethyl acetate for 30 min. The bar-to-bar RSD out with five different bars showed good results with RSD ≤ 15.6%, allowing the use of simultaneous extractions. LOD and LOQ values ranged from 3 to 15 ng L-1 and 10 to 50 ng L-1 respectively, and the determination coefficients were greater than 0.9869. The target analytes were not detected in the three analyzed samples. Therefore, the recovery study was performed fortifying the water samples. Analyte recovery ranged from 48.7 - 138.2% for drinking water, 40.2 - 128.2% for stream water and 67.5 - 128.7% for river water.

A green - high throughput -extraction method based on hydrophobic natural deep eutectic solvent for the determination of emerging contaminants in water by high performance liquid chromatography - diode array detection.

This study reports the use ofa natural deep eutectic solvent (NADES) with hollow fiber-microporous membrane liquid-liquid microextraction (HF-MMLLE) for the multiclass determination of 11 compounds classified as emerging contaminantsin water. Different deep eutectic solvents were synthetized and Thymol: Camphor (1:1 molar fraction) wasused as extraction solvent. The Thymol:Camphor was impregnated into the polypropylene membrane porous for 10 min, replacing commonly used solvents (ex. hexane and octanol). The optimized parameters were obtained by multi and univariate models. Extractions were carried out for 50 min using 1.5 mL of water sample at pH 6 and without addition of salt while desorption was made in a mixture of acetone: methanol (3:1, v/v) for 15 min. Separation/quantification was conducted by HPLC with a diode array detection (DAD)and calibration curves were obtained for each analyte. Determination coefficients higher than 0.9906 and limits of detection ranged from 0.3 to 6.1 µg L-1. Intraday precision (n = 3) ranged from 1.6 to 18.4% and inter day from 5.0 to 21.3%. Relative recoveries were performed in tap and stream water and ranged from 64 to 123%.

A natural and renewable biosorbent phase as a low-cost approach in disposable pipette extraction technique for the determination of emerging contaminants in lake water samples.

This study proposes an efficient analytical methodology using a biosorbent (cork) as an extraction phase in disposable pipette extraction technique for the rapid determination of the emerging contaminants methyl paraben, ethyl paraben, benzophenone, 3-(4-methylbenzylidene) camphor and 2-(ethylhexyl)-4-(dimethylamino) benzoate in lake water samples using high-performance liquid chromatography with diode array detection. The optimized conditions were comprised of 800 µL of sample, three cycles of 30 s each for the extraction, pH 6, addition of 30% w/v of NaCl. For the desorption step, the optimized desorption conditions were achieved with 100 µL of a mixture comprised of 50% methanol and 50% acetonitrile v/v, using one cycle of 30 s. Excellent analytical performance was achieved with limits of detection of 0.6 µg/L for methyl paraben to 1.4 µg/L for 3-(4-methylbenzylidene) camphor, and the limit of quantitation varied from 2 µg/L for methyl paraben to 4.3 µg/L 3-(4-methylbenzylidene) camphor, respectively. The correlation coefficients ranged from 0.9962 for ethyl paraben to 0.9980 for methyl paraben. The method accuracy varied from 71-132%, and the intraday precision ranged from 3 to 23% (n = 3) and interday from 9 to 23% (n = 9). The robustness was evaluated through Youden and Lenth's methods and indicated no significant variations in the results.

Development of a high-throughput method based on thin-film microextraction using a 96-well plate system with a cork coating for the extraction of emerging contaminants in river water samples.

In this study, a new method was developed in which a biosorbent material is used as the extractor phase in conjunction with a recently described sample preparation technique called thin-film microextraction and a 96-well plate system. The method was applied for the determination of emerging contaminants, such as 3-(4-methylbenzylidene) camphor, ethylparaben, triclocarban, and bisphenol A in water samples. The separation and detection of the analytes were performed by high-performance liquid chromatography with diode array detection. These contaminants are considered hazardous to human health and other living beings. Thus, the development of an analytical method to determine these compounds is of great interest. The extraction parameters were evaluated using multivariate and univariate optimization techniques. The optimum conditions for the method were 3 h of extraction time, 20 min of desorption with 300 µL of acetonitrile and methanol (50:50, v/v), and the addition of 5% w/v sodium chloride to the sample. The analytical figures of merit showed good results with linear correlation coefficients higher than 0.99, relative recoveries of 72-125%, interday precision (n = 3) of 4-18%, and intraday precision (n = 9) of 1-21%. The limit of detection was 0.3-5.5 µg/L, and the limit of quantification was 0.8-15 µg/L.

Evaluation of volatile profiles obtained for minimally-processed pineapple fruit samples during storage by headspace-solid phase microextraction gas chromatography-mass spectrometry

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.

A new configuration for bar adsorptive microextraction (BAµE) for the quantification of biomarkers (hexanal and heptanal) in human urine by HPLC providing an alternative for early lung cancer diagnosis.

In this paper, a remodeling of the bar adsorptive microextraction (BAµE) technique is proposed with impregnation of the derivatization reagent on the surface of the adsorptive bar containing a biosorbent material. The derivatization reagent was 2,4-dinitrophenylhydrazine (DNPH), which was adsorbed on the surface of the bar containing cork powder as the extractor phase for the determination of two aldehydes (hexanal and heptanal) which are known as lung cancer biomarkers in human urine samples. The derivatization reaction and the extraction occurred simultaneously on the surface of the bar (length 7.5 mm) under acidic conditions. The method optimization was carried out by univariate and multivariate analysis. The optimal conditions for the method were a DNPH to aldehydes ratio of 40:1, buffer solution of pH 4.0, extraction time of 60 min and liquid desorption of 10 min in 100 µL of acetonitrile. The aldehydes were analyzed by HPLC-DAD with a simple and fast (6 min) chromatographic run. The limits of detection (LODs) for hexanal and heptanal were 1.00 and 0.73 µmol L-1, respectively. The relative recoveries in urine samples ranged from 88 to 111% with relative standard deviations (RSDs) being less than 7%. The method developed is of low cost and can be successfully used for the quantification of these two lung cancer biomarkers in human urine samples, potentially providing an early diagnosis of lung cancer.