Dispersive Magnetic Solid-Phase Extraction as a Novelty Sample Treatment for the Determination of the Main Aflatoxins in Paprika.

Dispersive magnetic solid-phase extraction (DMSPE) technique is proposed as a new sensitive and effective sample treatment method for the determination of aflatoxins in paprika samples. DMSPE was followed by ultrahigh-performance liquid chromatography and high-resolution mass spectrometry detection (UHPLC-HRMS) using a non-targeted acquisition mode for the detection of main aflatoxins (aflatoxin G1, G2, B1 and B2) and derivatives. DMSPE was based on the use of magnetic nanocomposite coated with polypyrrole (PPy) polymer and the main experimental parameters influencing the extraction efficiency in adsorption and desorption steps have been studied and optimized. Analyses were performed using 250 µL magnetic PPy nanocomposite into the sample solution, adsorbing the analytes in 30 min and desorbing them with ethyl acetate (2 mL) in 15 min. The method has been validated, obtaining quantification limits between 3.5 and 4.7 µg kg-1 and recoveries between 89.5-97.7%. The high recovery rate, wide detection range and the use for the first time of the reusable Fe3O4@PPy nanomaterial in suspension for solid food matrices, guarantee the usefulness of the method developed for adequate control of aflatoxins levels in paprika. The proposed methodology was applied for the analysis of 31 samples (conventional and organic) revealing the absence of aflatoxins in the samples.

A rapid dispersive liquid-liquid microextraction of antimicrobial onion organosulfur compounds in animal feed coupled to gas chromatography-mass spectrometry.

A rapid analytical procedure is proposed for determining two antimicrobial onion organosulfur compounds, propyl disulfide (PDS) and propyl propane thiosulfonate (PTSO), in animal feed. The use of PTSO as a natural ingredient in animal feed is allowed due to its antimicrobial activity against pathogenic organisms. Two analytical methodologies using gas chromatography coupled to mass spectrometry (GC-MS) are compared. After the extraction of the compounds from animal feed with acetonitrile, dispersive solid phase extraction (DSPE) as a cleaning stage with C18, or dispersive liquid-liquid microextraction (DLLME), using 100 µL of CHCl3, was tried. Both the methods were validated using a pig feed sample and the best results were achieved by DLLME. This technique provided cleaner extracts, five-times greater linear ranges and lower detection limits than simple cleaning due to the enrichment factor achieved. The relative standard deviation decreased from 22% with DSPE to 13% with DLLME. The usefulness of the DLLME-GC-MS methodology was tested by analysing 10 different samples of chicken, calf, hen, cow and fish feed. The concentrations of PDS were in the 0.1-1.7 µg g-1 range and those of PTSO were between 0.09 and 2.1 µg g-1.

Determination of Cyanotoxins and Phycotoxins in Seawater and Algae-Based Food Supplements Using Ionic Liquids and Liquid Chromatography with Time-Of-Flight Mass Spectrometry.

An analytical procedure is proposed for determining three cyanotoxins (microcystin RR, microcystin LR, and nodularin) and two phycotoxins (domoic and okadaic acids) in seawater and algae-based food supplements. The toxins were first isolated by a salting out liquid extraction procedure. Since the concentration expected in the samples was very low, a dispersive liquid-liquid microextraction procedure was included for preconcentration. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate (80 mg) was used as green extractant solvent and acetonitrile as disperser solvent (0.5 mL) for a 10 mL sample volume at pH 1.5, following the principles of green analytical chemistry. Liquid chromatography with electrospray ionization and quadrupole time of flight-mass spectrometry (LC-Q-TOF-MS) was used. The selectivity of the detection system, based on accurate mass measurements, allowed the toxins to be unequivocally identified. Mass spectra for quadrupole time of flight-mass spectrometry (Q-TOF-MS) and Q-TOF-MS/MS were recorded in the positive ion mode and quantification was based on the protonated molecule. Retention times ranged between 6.2 and 17.9 min using a mobile phase composed by a mixture of methanol and formic acid (0.1%). None of the target toxins were detected in any of the seawater samples analyzed, above their corresponding detection limits. However, microcystin LR was detected in the blue green alga sample.

Determination of synthetic phenolic antioxidants in edible oils using microvial insert large volume injection gas-chromatography.

Three synthetic phenolic antioxidants, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT) and tert-butyl hydroquinone (TBHQ), were determined in different edible vegetable oil samples. The analyses were carried out by gas chromatography-mass spectrometry (GC-MS) using microvial insert large volume injection (LVI). Several parameters affecting this sample introduction step, such as temperatures, times and gas flows, were optimised. Quantification was carried out by the matrix-matched calibration method using carvacrol as internal standard, providing quantification limits between 0.08 and 0.10 ng g(-1), depending on the compound. The three phenolic compounds were detected in several of the samples, BHT being the most frequently found. Recovery assays for oil samples spiked at two concentration levels, 2.5 and 10 ng g(-1), provided recoveries in the 86-115% range.

Directly suspended droplet microextraction with in injection-port derivatization coupled to gas chromatography-mass spectrometry for the analysis of polyphenols in herbal infusions, fruits and functional foods.

A miniaturized liquid-phase extraction procedure based on directly suspended droplet microextraction is proposed for determining different classes of polyphenols. A derivatization reaction by means of in injection-port reaction with bis(trimethylsilyl)trifluoroacetamide is carried out to convert the polar non-volatile polyphenols into volatile derivatives. The separation and detection is carried out by coupling gas chromatography with mass spectrometry in the selected ion monitoring mode. The procedure uses undecanone, a low density organic solvent, and several factors influencing the extraction, collection efficiency and derivatization reaction are optimized. Excellent linearity was obtained for the range studied (0.05-500ngmL(-1)). The limits of detection are between 0.011 and 0.13ngmL(-1), depending on the compound, and the limits of quantification between 0.037 and 0.43ngmL(-1). The sensitivity and detection limits for polyphenols using the DSDME sample pretreatment method were very low. Enrichment factors are between 413 and 578. The recoveries obtained for spiked samples are satisfactory for all the compounds. The coupled miniaturized method is applied to the sensitive determination of both cis- and trans-resveratrol isomers, piceatannol, catechin, epicatechin, quercetin and fisetin in herbal infusions, fruits, juices and functional foods.

Use of headspace solid-phase microextraction coupled to liquid chromatography for the analysis of polycyclic aromatic hydrocarbons in tea infusions.

A sensitive and solvent-free procedure for the determination of 11 polycyclic aromatic hydrocarbons in tea infusions using headspace solid-phase microextraction coupled to liquid chromatography with fluorimetric detection is described. A medium polarity polydimethylsiloxane-divinylbenzene 60 microm fiber was found to be suitable for extraction at 90 degrees C and with an extraction time of 60 min under continuous stirring. Desorption was carried out using the static mode for 5 min. Under the optimized conditions, when 1.75 g of tea sample were extracted with boiling water, the precision ranged from 4 to 16% (RSD) and detection limits were between 4 and 145 ngL(-1), depending on the compound. The reliability of the procedure was corroborated by means of GC-MS. The results obtained for a standard reference material were within the range indicated by the supplier.