Thermal degradation of 2-furoic acid and furfuryl alcohol as pathways in the formation of furan and 2-methylfuran in food.

This study reports the heat-induced formation of furan by decarboxylation of 2-furoic acid, and 2-methylfuran by dehydration of furfuryl alcohol under dry conditions. Model systems were incubated at temperatures up to 190 °C, followed by quantitative determination of furan and 2-methylfuran performed by isotope dilution headspace gas chromatography-mass spectrometry. Results show that 2-furoic acid decarboxylation and furfuryl alcohol dehydration are activated as from about 140-160 °C. Furfuryl alcohol and 2-furoic acids were measured in a selection of roasted coffee products by isotope dilution liquid chromatography-high resolution mass spectrometry, and the data evidenced a strong correlation between the two compounds, suggesting an intimate mechanistic relationship between them. The possible oxidation of furfuryl alcohol to furfural and 2-furoic acid in heated food is raised with particular emphasis on coffee roasting. These findings are relevant for better understanding the formation of furan and alkylfurans in food, and ultimately opening avenues for mitigation.

Applications of capillary electrophoresis with chemiluminescence detection in clinical, environmental and food analysis. A review.

This paper reviews the latest developments and analytical applications of chemiluminescence detection coupled to capillary electrophoresis (CE-CL). Different sections considering the most common CL systems have been included, such as the tris(2,2'-bipyridine)ruthenium(II) system, the luminol and acridinium derivative reactions, the peroxyoxalate CL or direct oxidations. Improvements in instrumental designs, new strategies for improving both resolution and sensitivity, and applications in different fields such as clinical, pharmaceutical, environmental and food analysis have been included. This review covers the literature from 2010 to 2015.

Development of magnetic molecularly imprinted polymers for selective extraction: determination of citrinin in rice samples by liquid chromatography with UV diode array detection.

In this work, we report the synthesis of novel magnetic molecularly imprinted polymers (m-MIPs) and their application to the selective extraction of the mycotoxin citrinin (CIT) from food samples. The polymers were prepared by surface imprinting of Fe3O4 nanoparticles, using 2-naphtholic acid (2-NA) as template molecule, N-3,5-bis(trifluoromethyl)phenyl-N'-4-vinylphenyl urea and methacrylamide as functional monomers and ethyleneglycol dimethacrylate as cross-linker. The resulting material was characterized by transmission electron microscopy (TEM), and X-ray diffraction (XRD) and Fourier transform infrared spectroscopies (FT-IR). The polymers were used to develop a solid-phase extraction method (m-MISPE) for the selective recovery of CIT from rice extracts prior to its determination by HPLC with UV diode array detection. The method involves ultrasound-assisted extraction of the mycotoxin from rice samples with (7:3, v/v) methanol/water, followed by sample cleanup and preconcentration with m-MIP. The extraction (washing and elution) conditions were optimized and their optimal values found to provide CIT recoveries of 94-98 % with relative standard deviations (RSD) less than 3.4 % (n = 3) for preconcentrated sample extracts (5 mL) fortified with the analyte at concentrations over the range 25-100 µg kg(-1). Based on the results, the application of the m-MIPs facilitates the accurate and efficient determination of CIT in rice extracts.

High-throughput determination of citrinin in rice by ultra-high-performance liquid chromatography and fluorescence detection (UHPLC-FL).

A rapid, simple and effective method for the determination of citrinin in rice by UHPLC coupled to fluorescence detection has been developed and validated. Extraction of citrinin from rice samples was achieved by applying a QuEChERS-based extraction/partitioning process with water and acetonitrile, without the need of further extract clean-up. The method was fully validated for white rice, and its applicability in other rice matrices, such as brown and red rice, was confirmed by recovery experiments. Under optimum conditions, recoveries ranged from 72.5% to 92.8%, with relative standard deviations (RSDs) lower than 7.1%. Detection and quantification limits were estimated to be 1.5 and 5.0 µg kg(-1), respectively. Finally, 21 organic rice samples were analysed, but none was contaminated with citrinin above the detection limit of the method. The method proved to be fast and non-laborious.

Vortex-assisted surfactant-enhanced emulsification liquid-liquid microextraction for the determination of carbamates in juices by micellar electrokinetic chromatography tandem mass spectrometry.

A new method based on vortex-assisted surfactant-enhanced-emulsification liquid-liquid microextraction has been developed for the extraction of carbamate pesticides in juice samples prior to their determination by micellar electrokinetic chromatography coupled to tandem mass spectrometry. This sample treatment allowed the satisfactory extraction and the extract clean-up of 25 carbamates from different fruit and vegetal juices (banana, tomato, and peach). In this study, the addition of ammonium perfluorooctanoate in the aqueous sample in combination with vortex agitation, provided very clean extracts with short extraction times. Under optimized conditions, recoveries of the proposed method for these pesticides from fortified juice samples ranged from 81% to 104%, with relative standard deviations lower than 15%. Limits of quantification were between 2.3µgkg(-)(1) and 4.7µgkg(-)(1), showing the high sensitivity of this fast and simple method.

Simple and efficient methodology to determine mycotoxins in cereal syrups.

Consumption of cereal syrups is increasing nowadays. Mycotoxins may be found in syrups resulting from the use of contaminated raw material or invading microorganisms in the final manufactured product. However, these matrices have been scarcely explored regarding their mycotoxin content. A sensitive, simple and rapid method for the determination of ten mycotoxins (ochratoxin A, fumonisin B1, fumonisin B2, deoxynivalenol, fusarenon-X, T-2 and HT-2 toxin, citrinin, sterigmatocystin and zearalenone) in cereal syrups (rice, wheat and barley) has been developed and characterised using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) and a sample treatment based on QuEChERS procedure. Matrix-matched calibration curves were established and limits of quantification were below the limits usually established by current legislation in different foodstuff. The relative standard deviation of the whole analytical method was lower than 12% in all cases, while recoveries ranged from 70.2% to 100.6%, therefore fulfilling the current requirements for mycotoxins analysis.

Determination of carbamates in edible vegetable oils by ultra-high performance liquid chromatography-tandem mass spectrometry using a new clean-up based on zirconia for QuEChERS methodology.

In this study a fast, selective and sensitive multiresidue method based on QuEChERS methodology has been evaluated and validated for the determination of carbamate pesticides, in edible vegetable oils by UHPLC-MS/MS. A new clean-up sorbent, Supel(TM) QuE Z-Sep(+), has been successfully applied in vegetable oil extracts. Z-Sep(+) was compared with other sorbents (i.e. mixture of C18 and PSA) previously used for dispersive solid phase extraction of these matrices, reducing more effectively matrix effects without a significant decrease of analyte recoveries. Matrix effect was studied in different matrices (extra-virgin olive, sunflower, maize, linseed and sesame oil) being ≤│30│% for most of the studied pesticides. Under optimum conditions, recoveries ranged from 74% to 101%, with relative standard deviations lower than 10%. Limits of quantification ranged from 0.09 to 2.0 µg kg(-1), allowing their determination at the low concentration levels demanding by current legislation.

Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of carbamates in wines by ultra-high performance liquid chromatography-tandem mass spectrometry.

A new sensitive multiresidue method based on ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) has been developed for the detection, confirmation and quantification of twenty five carbamates in wine samples. The separation was achieved in 5.5 min, using a Zorbax Eclipse plus RRHD C18 column (50 mm×2.1 mm, 1.8 µm), with a mobile phase of water and methanol, both of them with 0.01% formic acid. The analytes were detected in positive mode with multiple reaction monitoring mode. Ultrasound-assisted surfactant-enhanced emulsification microextraction (UASEME), using a low-density extraction solvent has been optimized for the satisfactory extraction of carbamates and clean-up of extracts. The matrix effect was studied, showing that the proposed procedure provides very clean extracts. Under optimum conditions, recoveries for fortified wine samples ranged from 74 to 102%, with relative standard deviations lower than 6%. Limits of quantification ranged from 0.15 to 0.92 µgl(-1), showing the high sensitivity of this fast and simple method and its compliance with current requirements.

A new approach in sample treatment combined with UHPLC-MS/MS for the determination of multiclass mycotoxins in edible nuts and seeds.

A sensitive, simple and rapid method for the determination of fourteen mycotoxins in nuts and seeds (including almonds, peanuts, sunflower seeds, pumpkin seeds, walnuts, macadamia nuts, pistachios, hazelnuts and pine nuts) has been developed using ultra-high performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS). The sample treatment comprises a first step based on QuEChERS procedure for the determination of fumonisin B1, fumonisin B2, deoxynivalenol, fusarenon-X, T-2 and HT-2 toxin, citrinin, sterigmatocystin, zearalenone and ochratoxin A. A subsequent clean-up step based on the dispersive liquid-liquid microextraction (DLLME) was necessary for the determination of aflatoxins (B1, B2, G1 and G2), since their determination was not possible applying only the QuEChERS-based extraction. The method was validated for peanuts as representative matrix and was subsequently evaluated for the other eight matrices. Quantification limits obtained for aflatoxins, the unique mycotoxins legislated on these matrices, were lower than the maximum levels allowed by the current legislation, while quantification limits obtained for the other mycotoxins were lower than the limits usually permitted by the legislation in other food matrices. Precision of the method was always lower than 11%, and recoveries ranged between 60.7% and 104.3%.

Chemiluminescence detection in liquid chromatography: applications to clinical, pharmaceutical, environmental and food analysis--a review.

Chemiluminescence (CL)-based detection has become in the last years quite a useful detecting tool in liquid chromatography (HPLC) due to its simplicity, low cost and high sensitivity and selectivity, and the development in instrumentation. Minimal instrumentation is required and no external light source is needed; thus, the optical system is quite simple. As a consequence, a wide variety of analytical methods have been developed in clinical, pharmaceutical, environmental and food analysis. In this review, applications of the HPLC-CL coupling in those different fields have been included and classified in relation to the different CL systems employed (namely peroxyoxalate reaction, tris(2,2'-bipyridine) ruthenium (II) reaction, luminol system and direct oxidations) and also sub-classified according to the group of analyte. The review covers the literature from 2000 until the end of 2008.

Simultaneous identification of natural dyes in the collection of drawings and maps from The Royal Chancellery Archives in Granada (Spain) by CE.

A simple and rapid capillary electrophoretic method with UV detection (CE-UV) has been developed for the identification of five natural dyes namely, carmine, indigo, saffron, gamboge and Rubia tinctoria root. The separation was performed in a fused-silica capillary of 64.5 cm length and 50 microm id. The running buffer was 40 mM sodium tetraborate buffer solution (pH 9.25). The applied potential was 30 kV, the temperature was 25 degrees C and detections were performed at 196, 232, 252, 300 and 356 nm. The injections were under pressure of 50 mbar during 13 s. The method was applied to the identification of carminic acid, gambogic acid, crocetin, indigotin, alizarin and purpurin in the collection of drawings and maps at the Royal Chancellery Archives in Granada (Spain). The method was validated by using HPLC as a reference method.

Determination of the herbicide metribuzin and its major conversion products in soil by micellar electrokinetic chromatography.

In this paper, a multiresidue method for the analysis in soils of metribuzin (M) and its major conversion products, deaminometribuzin (DA), diketometribuzin (DK) and deaminodiketometribuzin (DADK) is developed. Considering the neutral and charged nature of the molecules, micellar electrokinetic chromatography (MEKC) is a very efficient method for the separation of these compounds, providing high efficiency and short analysis times. Different electrophoretic parameters were studied to optimize the separation, such as the buffer pH and concentration, sodium dodecyl sulphate (SDS) concentration, injection conditions and applied voltage. Excellent separation of the studied compounds was achieved within about 7 min. Soil samples were previously extracted using methanol in an ultrasonic bath and then a SPE procedure was applied to pre-concentrate the analytes by passage through a LiChrolut EN sorbent column. Detection limits at the low microgkg(-1) level were obtained. The proposed method has been satisfactorily applied in soil samples showing recoveries ranging from 86.7% to 104.2% and represents a valuable alternative to high-performance liquid chromatography (HPLC).

Establishment of signal-recovery functions for calculation of recovery factor. Application to monitoring of contaminant residues in vegetables by chemiluminescence detection.

A new strategy is proposed for verifying if recovery factor is constant and independent of the real analyte content of samples. A signal-recovery function has been developed on the basis of measurement of spiked test samples before and after a pre-treatment step and considering, as starting point, a recent IUPAC recommendation which distinguishes between two terms--recovery factor, R, and apparent recovery, R*. Apparent recovery includes recovery factor and a new recovery term proposed in a previous paper by the authors, named calibration recovery, R(C). The signal-recovery function is obtained directly from the measured analytical signals instead of from the concentrations, simplifying the calculations. A linear signal-recovery curve indicates that the recovery factor is constant in the analyte concentration range studied experimentally and, in this way, a single recovery factor can be calculated. The usefulness of the proposed method has been shown by quantification of the pesticide carbaryl by two different flow-injection analysis methods with chemiluminescent detection based on the luminol and TCPO systems. Good results were obtained from both methods.