Search

This study developed a new effervescence-assisted switchable fatty acid-based microextraction combined with solidification of a floating organic-droplet (EA-SFAM-SFO) for simple and rapid determination of fluoroquinolones and tetracyclines in seawater, sediment, and seafood. Five medium-chain fatty acids (pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid) were tested as an extraction solvent, given their ability to change between hydrophobic and hydrophilic forms by pH adjustment. As nonanoic acid had the highest extraction recovery (>92%) for the six antibiotics and the ability to transform from liquid to a solidified floating state at low temperature, it was selected as the optimum extraction solvent. The prominent advantages of the newly developed method are: (1) reaction between the procedures salt and fatty acid changed extraction solvent from the hydrophobic to hydrophilic state; (2) bubbling with CO 2 greatly increased the contact area between fatty acid and analytes resulting in improved extraction recovery; and (3) solidification of the fatty acid at a low temperature provided good separation and avoided the use of specialized equipment. Single-factor screening and optimization of the main factors were conducted using Plackett-Burman design and central composite design, respectively. The main parameters were optimized as follows: 258 μL fatty acid, 406 μL H 2 SO 4 (98%), 3.9 min vortex time, and 354 μL Na 2 CO 3 (2 mol L - 1). Under optimized conditions, limits of detection were 0.007-0.113 μg L -1 or μg kg -1 and extraction recoveries were 82.2%-116.7% for six fluoroquinolone and tetracycline antibiotics in seawater, sediments, and seafood. The newly developed method combines the advantages of effervescence-assisted dispersion, hydrophobic/hydrophilic switchable solvent, and liquid/solid transition induced by low temperature. Overall, the new method is simple, quick, and environment-friendly with low detection limits and high recoveries. Thus, the newly developed method has excellent prospects for sample pretreatment and analysis of antibiotics in marine environmental and food samples. Graphical Abstract ᅟ.

A simple, rapid, and efficient ultrasound-assisted dispersive liquid-liquid microextraction (US-DLLME) method was developed for extraction of tetracycline residues from egg supplement samples, with subsequent determination by flow injection analysis (FIA) coupled to a liquid waveguide capillary cell (LWCC) and a controlled temperature heating bath. Tetracyclines react with diazotized p-sulfanilic acid, in a slightly alkaline medium, to form azo compounds that can be measured at 435 nm. The reaction sensitivity improved substantially (5.12-fold) using an in-line heating temperature of 45 °C. Multivariate methodology was used to optimize the factors affecting the extraction efficiency, considering the volumes of extraction and disperser solvents, sonication time, extraction time, and centrifugation time. Good linearity in the range 30-600 μg L(-1) was obtained for all the tetracyclines, with regression coefficients (r) higher than 0.9974. The limits of detection ranged from 6.4 to 11.1 μg L(-1), and the recoveries were in the range 85.7-96.4 %, with relative standard deviation lower than 9.8 %. Analyte recovery was improved by approximately 6 % when the microextraction was assisted by ultrasound. The results obtained with the proposed US-DLLME-FIA method were confirmed by a reference HPLC method and showed that the egg supplement samples analyzed were suitable for human consumption.

A new, fast, and environmentally friendly method based on ultrasound assisted extraction combined with dispersive liquid-liquid microextraction (US-DLLME) was developed and optimized for assessing the levels of seven phthalate metabolites (including the mono(ethyl hexyl) phthalate (MEHP), mono(2-ethyl-5-hydroxyhexyl) phthalate (5-OH-MEHP), mono(2-ethyl-5-oxohexyl) phthalate (5-oxo-MEHP), mono-n-butyl phthalate (MnBP), mono-isobutyl phthalate (MiBP), monoethyl phthalate (MEP), and mono-benzyl phthalate (MBzP)) in human nails by UPLC-MS/MS. The optimization of the US-DLLME method was performed using a Taguchi combinatorial design (L9 array). Several parameters such as extraction solvent, solvent volume, extraction time, acid, acid concentration, and vortex time were studied. The optimal extraction conditions achieved were 180 μL of trichloroethylene (extraction solvent), 2 mL trifluoroacetic acid in methanol (2 M), 2 h extraction and 3 min vortex time. The optimized method had a good precision (6-17 %). The accuracy ranged from 79 to 108 % and the limit of method quantification (LOQm) was below 14 ng/g for all compounds. The developed US-DLLME method was applied to determine the target metabolites in 10 Belgian individuals. Levels of the analytes measured in nails ranged between <12 and 7982 ng/g. The MEHP, MBP isomers, and MEP were the major metabolites and detected in every sample. Miniaturization (low volumes of organic solvents used), low costs, speed, and simplicity are the main advantages of this US-DLLME based method. Graphical Abstract Extraction and phase separation of the US-DLLME procedure.

A simple, rapid, and sensitive method based on simultaneous protein precipitation and extraction of aflatoxin M1 (AFM1) followed by dispersive liquid-liquid microextraction (DLLME) and ultrahigh pressure liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) analysis was developed for the determination of AFM1 in milk samples. In order to precipitate the proteins and extract AFM1 from milk, a sample pretreatment using acetonitrile and NaCl as the extraction/denaturant solvent and salting-out agent, respectively, was optimised. Subsequently, the acetonitrile (upper) phase, containing AFM1, was used as the disperser solvent in DLLME, and extractant (chloroform) and water were added in turn to the extract to perform the DLLME process. The main parameters affecting the extraction efficiency of the whole analytical procedure, such as acetonitrile volume, amount of salt, type and volume of extractant and water volume, were carefully optimised by experimental design. Under optimum conditions, the developed method provides an enrichment factor of 33 and detection and quantification limits (0.6 and 2.0 ng kg(-1), respectively) below the maximum levels imposed by current regulations for AFM1 in milk and infant milk formulae. Recoveries (61.3-75.3%) and repeatability (RSD < 10, n = 3), tested in different types of milk at four AFM1 levels, met the performance criteria required by EC Regulation No. 401/2006. Moreover, the matrix effect on the signal intensity of the analyte was negligible. The proposed method provides a rapid extraction and an accurate determination of AFM1 in milk and formula milk using a simple and inexpensive sample preparation procedure.

A rapid, simple, and efficient method for the fast determination of multiple phytohormones was developed in this work, based on single-drop liquid-liquid-liquid microextraction (SD-LLLME) combined with direct analysis in real-time mass spectrometry (DART-MS). Six phytohormones--indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), jasmonic acid (JA), salicylic acid (SA), abscisic acid (ABA), and gibberellin A(3) (GA(3))--were analyzed simultaneously using this method, and the conditions employed for DART-MS and SD-LLLME were optimized systematically. Satisfactory results were obtained in terms of linearity (R (2) values for all phytohormones were 0.991-0.996), sensitivity (limits of detection were 0.65-72 ng/mL), and repeatability (RSD values were 6.9-14%). In addition, the proposed method was applied to determine the endogenous phytohormones in three kinds of fruit juice. Different concentrations of phytohormones were detected with satisfactory recoveries, and the whole analytical procedure took no more than 30 min. Therefore, this combination of SD-LLLME and DART-MS was shown to be a suitable and effective approach for the fast analysis of targets present at trace level concentrations in complex matrices.

A rapid, sensitive and environmentally friendly method for the analysis of 14 anilines in water samples by dispersive liquid-liquid microextraction based on solidification of floating organic drop (DLLME-SFO) prior to gas chromatography-mass spectrometry (GC-MS) was developed and optimized. In the proposed method, cyclohexane was used as the extraction solvent as its toxicity was much lower than that of the solvent usually used in dispersive liquid-liquid microextraction (DLLME). In the optimized conditions, the method exhibited good analytical performance. Based on a signal-to-noise ratio of 3, limits of detection for anilines were in the range of 0.07 to 0.29 μg L(-1), and the linear range was 0.5-200 μg L(-1) with regression coefficients (r(2)) higher than 0.9977. It was efficient for qualitative and quantitative analysis of anilines in water samples. The relative standard deviations varied from 2.9 to 8.6% depending on different compounds indicating good precision. Tap water and river water were selected for evaluating the application to real water samples. The relative recoveries of anilines for the two real samples spiked with 10 μg L(-1) anilines were in the scope of 78.2-114.6% and 77.3-115.6%, respectively.

A simple and rapid dispersive liquid-liquid microextraction method has been developed for the determination of 11 benzotriazoles and benzothiazoles in water samples. Tri-n-butylphosphate (TBP) was used as extractant, thus avoiding the use of toxic water-immiscible chlorinated solvents. The influence of several variables (e.g., type and volume of dispersant and extraction solvents, sample pH, ionic strength, etc.) on the performance of the sample preparation step was systematically evaluated. Analytical determinations were carried out by high-performance liquid chromatography with fluorescence and UV detection and liquid chromatography-electrospray ionization-tandem mass spectrometry. The optimized method exhibited a good precision level with relative standard deviation values between 3.7% and 8.4%. Extraction yields ranging from 67% to 97% were obtained for all of these considered compounds. Finally, the proposed method was successfully applied to the analysis of benzotriazoles and benzothiazoles in real water samples (tap, river, industrial waters, and treated and raw wastewaters).