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URI permanente para esta colecciónhttps://hdl.handle.net/10953/276

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Ambient (desorption/ionization) mass spectrometry methods for pesticide testing in food: a review
Beneito-Cambra, Miriam; Gilbert-López, Bienvenida; Moreno-González, David; Bouza, Marcos; Franzke, Joachim; García-Reyes, Juan Francisco; Molina-Díaz, Antonio
Ambient mass spectrometry refers to the family of techniques that allows ions to be generated from condensed phase samples under ambient conditions and then, collected and analysed by mass spectrometry. One of their key advantages relies on their ability to allow the analysis of samples with minimal to no sample workup. This feature maps well to the requirements of food safety testing, in particular, those related to the fast determination of pesticide residues in foods. This review discusses the application of different ambient ionization methods for the qualitative and (semi)quantitative determination of pesticides in foods, with the focus on different specific methods used and their ionization mechanisms. More popular techniques used are those commercially available including desorption electrospray ionization (DESI-MS), direct analysis on real time (DART-MS), paper spray (PSMS) and low-temperature plasma (LTP-MS). Several applications described with ambient MS have reported limits of quantitation approaching those of reference methods, typically based on LC-MS and generic sample extraction procedures. Some of them have been combined with portable mass spectrometers thus allowing “in situ” analysis. In addition, these techniques have the ability to map surfaces (ambient MS imaging) to unravel the distribution of agrochemicals on crops.
Ambient Diode Laser Desorption Dielectric Barrier Discharge Ionization Mass Spectrometry of Nonvolatile Chemicals
(ACS Publications, 2013-02-19) Gilbert-López, Bienvenida; Schilling, Michael; Alhmann, Norman; Michels, Antje; Hayen, Heiko; Molina-Díaz, Antonio; García-Reyes, Juan Francisco; Franzke, Joachim
In this work, the combined use of desorption by a continuous wave near-infrared diode laser and ionization by a dielectric barrier discharge-based probe (laser desorption dielectric barrier discharge ionization mass spectrometry (LD-DBDI-MS)) is presented as an ambient ionization method for the mass spectrometric detection of nonvolatile chemicals on surfaces. A separation of desorption and ionization processes could be verified. The use of the diode laser is motivated by its low cost, ease of use, and small size. To achieve an efficient desorption, the glass substrates are coated at the back side with a black point (target point, where the sample is deposited) in order to absorb the energy offered by the diode laser radiation. Subsequent ionization is accomplished by a helium plasmajet generated in the dielectric barrier discharge source. Examples on the application of this approach are shown in both positive and negative ionization modes. A wide variety of multiclass species with low vapor pressure were tested including pesticides, pharmaceuticals and explosives (reserpine, roxithromycin, propazine, prochloraz, spinosad, ampicillin, dicloxacillin, enrofloxacin, tetracycline, oxytetracycline, erythromycin, spinosad, cyclo-1,3,5,7-tetramethylene tetranitrate (HMX), and cyclo-1,3,5-trimethylene trinitramine (RDX)). A comparative evaluation revealed that the use of the laser is advantageous, compared to just heating the substrate surface.
Analytical pyrolysis (Py-GC-MS) for the assessment of olive mill pomace composting efficiency and the effects of compost thermal treatment
(Elsevier, 2022) Peña-Rueda, Marta; Comino-Romero, Francisco; Aranda-Sanjuán, Víctor; Domínguez-Vidal, Ana; Ayora-Cañada, María José
Composting is an interesting solution for recycling the large amount of residues typically generated in olive oil production areas, particularly olive mill pomace. Bulking agents must be added to wet olive mill pomace for composting. The diversity of the materials used (such as olive tree-pruning residues, animal manure, or straw) and the variable proportion, in which they are mixed, are responsible for the heterogeneity and variability of the quality of the produced compost. For this reason, a comprehensive characterization of compost organic matter is necessary to gain information about its stability and maturity useful as well as to predict its behavior as a soil amendment. In this work, fresh olive mill pomace and four composted olive mill pomace samples were characterized using analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC-MS). Results showed a large variety of pyrolysis products, many of which had a specific biochemical origin. Pyrolysis-GC-MS revealed a decrease in fatty acids and aliphatic compounds content with composting, along with carbohydrates degradation and an increase in phenolic and N-compounds levels. Furthermore, the differences observed in organic matter characteristics had an impact on agronomic aspects (water repellency and phytotoxicity). Thus, the occurrence of fatty acids in incompletely composted materials (mainly palmitic and cis-vaccenic acids) was associated with increased phytotoxicity and higher water repellency. The presence of chicken manure in the mixtures was proved to favor the humification process and the production of stabilized compost (characterized by a lower Aliphatic-C/Aromatic-C ratio and higher N-heterocycles content). Furthermore, in this work, the effectiveness of applying thermal treatments to improve compost quality has been evaluated. Analysis of the Py-GC-MS results by means of principal component analysis (PCA) revealed thermal rearrangement, predominantly aromatization, and loss of functional groups of carbohydrates, lignin, and proteins, at temperatures above 225 ºC. Interestingly, the results suggest that materials with a non-effective or incomplete composting process can be transformed by thermal treatment into more stable products, exhibiting similar agronomic characteristics as those have that undergone a more efficient biotransformation.
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
(Elsevier, 2014-10) Moreno-González, David; Huertas-Pérez, José F.; García-Campaña, Ana M.; Gámiz-Gracia, Laura
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, SupelTM 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.
Evaluation of hydrophilic interaction liquid chromatography–tandem mass spectrometry and extraction with molecularly imprinted polymers for determination of aminoglycosides in milk and milk-based functional foods
(Elsevier, 2017-08-15) Moreno-González, David; Hamed, Ahmed M.; García-Campaña, Ana M.; Gámiz-Gracia, Laura
An analytical method for the determination of eleven aminoglycosides in different types of milk and milk-based functional products has been optimized and validated. A hydrophilic interaction chromatography (HILIC) column was proposed for the separation of analytes by ultra-high performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS). A commercially molecularly imprinted polymer has been used for the solid phase extraction of the analytes, in order to achieve high selectivity in the sample treatment. The proposed method was characterized for different types of milk (whole cow milk, skimmed cow milk, whole goat milk) and functional dairy products, such as follow-on milk, Omega 3-enriched milk and isoflavones-enriched milk. Matrix effect was studied in the different matrices, being lower than │15│% in all cases, showing that the proposed procedure provided very clean extracts. Limits of quantification in the range 4.2–49 µg kg−1 were estimated, well below the maximum residue limits established by the European Union. Recoveries ranged from 70% to 106% with RSD lower than 13%, in compliance with the current legislation. The combination of HILIC to solve the difficulties of the separation of these very polar compounds in reverse phase with the use of MISPE for sample treatment and MS/MS detection provided a very sensitive, highly selective, robust and useful method for identification and quantification of aminoglycoside residues in different types of milk and milk-based products.
Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography
(Elsevier, 2018-03) Rocío-Bautista, Priscilla; Pino, Verónica; Pasán, Jorge; López-Hernández, Irene; Ayala-Díaz, Juan; Ruiz-Pérez, Catalina; Afonso, Ana M.
Five metal-organic frameworks (MOFs), specifically HKUST-1, MOF-5(Zn), MIL-53(Al), UiO-64 and MOF-74(Zn) are synthesized, characterized, and utilized in a miniaturized solid-phase extraction method under dispersive mode (D-µSPE) for the determination of six pollutants of different nature, including one polycyclic aromatic hydrocarbon, two hormones, two drugs, and one disinfectant, from environmental waters (tap water and wastewater). A discussion of possible interactions justifying the partitioning of target analytes to the MOFs is included, considering not only the analytes’ physicochemical characteristics but also those of MOFs: metal nature, structural environment of MOF pores, pore size and pore aperture widths, among others. MIL-53(Al) is selected for its versatility and high extraction efficiency for the target compounds. The D-µSPE method using MIL-53(Al) is optimized and used in combination with high-performance liquid chromatography (HPLC) with diode array detector (DAD) or liquid-chromatography with time-of-flight mass spectrometric detector (LC-TOF). Under optimum conditions, only 5 mg of MIL-53(Al) are required for 10 mL of water, with the aid of 5 min of vortex and 5 min of centrifugation. Elution is accomplished with 200 µL of acetonitrile (3 times), and evaporation down to 100 µL before LC injection. Detection limits down to 0.040 μg L−1 for triclosan and 0.013 μg L−1 for atrazine are obtained for the entire method using HPLC-DAD and LC-TOF, respectively. The method, operating at low spiked levels (2 µg L−1 for HPLC-DAD and 0.7 µg L−1 for LC-TOF), is also characterized for average relative recoveries of 109% and 105%; relative standard deviation values lower than 8.7% and 7.5%; and average extraction efficiencies of 41.2% and 49.1%; using HPLC-DAD and LC-TOF, respectively; while demonstrating adequate analytical performance with complex samples such as wastewaters.
Micellar electrokinetic chromatography–electrospray ionization mass spectrometry employing a volatile surfactant for the analysis of amino acids in human urine
(Wiley, 2013-09) Moreno-González, David; Sastre Toraño, Javier; Gámiz-Gracia, Laura; García-Campaña, Ana M.; de Jong, Gerhardus J.; Somsen, Govert W.
A new MEKC-ESI-MS method for the analysis of amino acids (AAs) in human urine was developed employing ammonium perfluorooctanoate (APFO) as volatile surfactant. The influence of APFO on the MS signal of AAs was evaluated by infusion experiments, which showed that APFO hardly affects analyte responses and presents significantly less ion suppression than equal concentrations of ammonium acetate. In order to obtain efficient separation of AAs, MEKC parameters such as the pH and APFO concentration of the BGE, were optimized. Optimum AA resolution, including baseline separation of leucine and isoleucine, was obtained using 150 mM APFO (pH 9.0) as BGE, representing a considerable selectivity improvement over CE using 50 mM ammonium acetate (pH 9.0). Optimization of CE-MS parameters, such as sheath liquid composition and flow rate, and ESI and MS settings, led to LODs ranging from 9 to 26 ng/mL for the 20 tested AAs, which is highly favorable for an MEKC-MS method. Good linearity (r2 > 0.99) and repeatability were obtained for all AAs tested with RSD values of 3.0–6.7% for peak area and <1.5% for migration time. The applicability of the MEKC-MS method was demonstrated by the quantitative determination of AAs in urine employing only a 1:1 dilution with BGE as sample pretreatment. All AAs could selectively be detected and quantified obtaining relevant concentration values for normal human urine.
Microfluidic water-assisted trap focusing method for ultra-large volume injection in reversed-phase nano-liquid chromatography coupled to electron ionization tandem-mass spectrometry
(Elsevier, 2020-09) Termopoli, Veronica; Famiglini, Giorgio; Vocale, Palma; Morini, Gian Luca; Palma, Pierangela; Rocío-Bautista, Priscilla; Mansoor, Saeed; Perry, Simon; Cappiello, Achille
Herein we present an efficient, column-switching method that relies on a custom-made T-union passive diffusion micromixer to assist water dilution and promote trap solute focusing of a high sample volume dissolved in pure organic solvent using a 0.075 mm i.d. nano-LC column. This method allows injecting 20 μL (or higher) of sample volume, speeding up the analysis time, with a 400-fold increase of the limits of quantitation for selected compounds. Five pesticides in different media were used as model compounds, and the analyses were carried out with a triple quadrupole mass spectrometer equipped with a Liquid Electron Ionization (LEI) LC-MS interface working in multiple reaction monitoring (MRM) mode. The system microfluidics were investigated using COMSOL modeling software. Robustness of the entire system was evaluated using a post-extraction addition soil extracts with limits of detection values spanning from 0.10 to 0.45 µg/L. Reproducible results in terms of peak area, peak shape, and retention times were achieved in soil matrix. Repeatability test on peak area variations were lower than 10%.
Molecularly imprinted polymer as in-line concentrator in capillary electrophoresis coupled with mass spectrometry for the determination of quinolones in bovine milk samples
(Elsevier, 2014-09) Moreno-González, David; Lara, Francisco J.; Gámiz-Gracia, Laura; García-Campaña, Ana M.
In this work molecularly imprinted polymers have been evaluated as sorbent for the construction of an in-line solid phase extraction analyte concentrator in capillary electrophoresis coupled with mass spectrometry for the determination of the eight regulated veterinary quinolones in bovine milk samples. Different parameters affecting the analyte concentrator performance, such as sample pH, volume and composition of the elution plug and injection time, were studied. Sample volumes of 22 μL (2 bar for 15 min) were loaded on the MISPE microcartridge and the retained analytes were eluted by injecting a plug of MeOH/H2O/NH3 (60/37/3 by volume) for 125 s at 50 mbar (60 nL). The proposed method is simple for the monitoring of these antibiotic residues in milk samples, allowing the direct injection of the samples with minimum sample pretreatment, achieving limits of detection between 3.8 and 4.7 μg kg−1 and unequivocal identification of the compounds working in tandem mass spectrometry. Recoveries ranging from 70.0 to 102.3% were obtained and satisfactory intra-day and inter-day RSDs were achieved (≤12% and 15% respectively). Reproducibility among different constructed analyte concentrators showed RSD ≤ 11%
Multi-residue pesticide analysis in virgin olive oil by nanoflow liquid chromatography high resolution mass spectrometry
(Elsevier, 2018-08-10) Moreno-González, David; Alcántara-Durán, Jaime; Addona, Silvina M.; Beneito-Cambra, Miriam
In this article, a nanoflow liquid chromatography system coupled to high resolution mass spectrometry (nanoflow LC/ESI Q-Orbitrap-MS) has been applied for the development of a multiresidue pesticide method for the determination of 162 multiclass pesticides in olive oil samples. Due to the relatively high lipid content of the raw QuEChERS acetonitrile extracts obtained from this type of fatty vegetable samples, a dispersive solid phase extraction (dSPE) sorbent proposed to retain both fatty acids and triglycerides, namely Enhanced Matrix Removal-Lipid (EMR-Lipid) has been implemented as additional cleanup step. The analytical performances of the proposed method were evaluated,achieving recoveries in the range 75–119% with relative standard deviations lower than 19% (n = 6). The dSPE sorbent allowed the removal of most coextracted interferences without a significant loss of analytes. Matrix effects were also evaluated, showing a negligible effect for most of the compounds tested, when a dilution factor of 50 was applied. Notably, despite the use of relatively high dilution factors (e.g. 1:50) to minimize matrix effects, the lowest concentration levels detected with this method – in the low μg kg−1 range – are well below the corresponding maximum residue levels established by the current European legislation
Parentucellia latifolia subsp. latifolia: A potential source for loganin iridoids by HPLC-ESI-MSn technique
(Elsevier, 2019) Llorent-Martínez, Eulogio; Fernández-de-Córdova, María Luisa; Zengin, Gokhan; Bahadori, Mir Babak; Aumeeruddy, Muhammad Zakariyyah; Rengasamy, Kannan RR; Mahomoodally, Mohamad Fawzi
This study attempts to compare the pharmaceutical potential (antioxidant and key enzyme inhibition of clinical relevance) of organic and aqueous extracts of Parentucellia latifolia (L.) Caruel subsp. latifolia (L.) Caruel as well as phytochemical composition. The phytochemical compounds were evaluated by spectrophotometric methods (for total amounts) and HPLC-ESI-DAD-MSn (for individual compounds). The extracts were screened for antioxidant abilities by in vitro assays. Inhibition effects were also investigated against a set of enzymes linked to major health problems. Generally, the methanol (MeOH) and aqueous extracts displayed higher scavenging abilities on radicals and reductive effects when compared with the ethyl acetate (EtOAc) extract. On the other hand, the EtOAc extract was the most active inhibitor on cholinesterases (1.81–1.88 mg GALAE/g), amylase (0.70 mmol ACAE/g), glucosidase (2.85 mmol ACAE/g) and lipase (33.24 mg OE/g). The highest TPC was observed in the aqueous extract (25.07 mg GAE/g) while MeOH extract possessed the highest level of TFC (44.15 mg RE/g) and TPAC (3.46 mg CE/g). LC-MSn metabolite profiling indicated that loganin and its isomers, rutin, and luteolin-O-hexoside were the most abundant compounds. Our results suggest that P. latifolia may be valuable source of phytoagentsfor the management of noncommunicable diseases.
Phenolic Analysis and In Vitro Biological Activity of Red Wine, Pomace and Grape Seeds Oil Derived from Vitis vinifera L. cv. Montepulciano d’Abruzzo
(MDPI, 2021-10-27) Mollica, Adriano; Scioli, Giuseppe; Della Valle, Alice; Cichelli, Angelo; Novellino, Ettore; Bauer, Marta; Kamysz, Wojciech; Llorent-Martínez, Eulogio ; Fernández-de-Córdova, María Luisa; Castillo-López, Roxana; Ak, Gunes; Zengin, Gokhan; Pieretti, Stefano; Stefanucci, Azzurra
Background: Grape pomace is commonly considered a waste product of monovarietal red wine production. Methods: HPLC-DAD analysis was performed to determine the polyphenol and flavonoid contents of all the extracts obtained from Montepulciano d’Abruzzo red wine and grape skins whereas, GC-MS was applied to the determination of fatty acid composition in grape seeds oil. Biological characterization involves antioxidant and antimicrobial assays for all the extracts and seeds oil; Their ability to inhibit α-glucosidase, α-amylase, α-tyrosinase, and ChE enzymes was also detected, together with anti-inflammatory activity on wine, grape skin extracts, and seeds oil by lipoxygenase (5-LOX) and LPS-stimulated macrophage release assays. Results: Data indicate significative polyphenols content (199.31 ± 7.21 mgGAE/g), antioxidant (CUPRAC assay (1036.98 mgTE/g)), enzymatic inhibition (α-tyrosinase: 151.30 ± 1.20 mgKAE/g) and anti-inflammatory activities for wine-organic extract 2, while the antimicrobial activity of grape skin decoction is higher than those reported by wine extracts on three bacterial strains. Interestingly only dealcoholized wine and wine-aqueous extract exerts inhibitory effects on α-glucosidase (20.62 ± 0.23 mmolACAE/g and 19.81 ± 0.03 mmolACAE/g, respectively), while seeds oil is rich in oleic and linoleic acids. Conclusions: These results confirm the strong antioxidant properties of Montepulciano d’Abruzzo grape pomace, suggesting the potential use of this waste product as functional food supplements in the human diet and in cosmeceutics.
Preliminary phytochemical screening and antioxidant activity of commercial Moringa oleifera food supplements
(MDPI, 2023-01-02) Llorent-Martínez, Eulogio J.; Gordo-Moreno, Ana I.; Fernández-de Córdova, María Luisa; Ruiz-Medina, Antonio
Moringa oleifera has been reported to possess a high number of bioactive compounds; hence, several food supplements are commercially available based on it. This work aimed to analyze the phytochemical composition and antioxidant activity of commercial food supplements. The phenolic composition of methanolic extracts was determined by using high-performance liquid chromatography with diode-array and electrospray ionization mass spectrometric detection (HPLCDAD- ESI-MSn), and the antioxidant activity was assessed by ABTS + and DPPH assays. Thirty-three compounds were identified, and all the main compounds were quantified, observing that the main contribution to the phenolic profile was due to kaempferol and quercetin glucosides. The antioxidant activity in both assays agreed with the phenolic content: the higher the phenolic levels, the higher the antioxidant activity. The obtained results were compared with those previously published regarding Moringa oleifera leaves to establish the potential benefits of food supplement consumption in the diet.
Raman and Fourier transform infrared microspectroscopies reveal medieval Hispano–Muslim wood painting techniques and provide new insights into red lead production technology
(Wiley, 2019) Arjonilla, Paz; Domínguez-Vidal, Ana; Correa, Elena; Domene-Ruiz, María José; Ayora-Cañada, María José
This paper describes the study of two Nasrid polychrome wooden ceilings from the Alhambra monumental ensemble using vibrational spectroscopic techniques. The study is focused on the identification of the constituent materials and execution techniques used employing non‐invasive and non‐destructive scientific investigation methods. Information about both inorganic (pigments) and organic (binders and coatings) materials has been obtained without the need for time‐consuming procedures. A complex stratigraphy involving the use of a protective priming layer of red lead covered with animal glue and white lead was revealed. The identification of Raman signatures of different lead oxide compounds, including lead‐tin oxide (Pb2SnO4), in the priming layer, allowed us to hypothesize the synthesis of red lead (Pb3O4) from litharge (α‐PbO), a common by‐product of the cupellation process used since antiquity for silver production. Furthermore, the pigments employed in hidden drawings found in the reverse of the wood pieces of one of the ceilings were also studied and compared with those found in the visible external face.
Self-assembly structures of 1H-indazoles in solution and solid phases: A vibrational (IR, FarIR, Raman and VCD) and computational study
(Wiley, 2013) Avilés-Moreno, Juan Ramón; Quesada-Moreno, María del Mar; López-González, Juan Jesús; Claramunt, Rosa M.; López-García, Concepción; Alkorta, Ibon; Elguero, José
1H-indazoles are good candidates to study phenomena of molecular association and spontaneous resolution of chiral compounds. Thus, because the 1H-indazoles can crystallize forming dimers, trimers or catemers, depending on their structure and the phase where they are, the difficulty of the experimental analysis of the structure of the family of 1H-indazoles is clear. This lead to contemplate several questions: How can we determine the presence of different structures of a determined molecular species if they change according to the phase? Could these different structures be present in the same phase simultaneously? How can it be determined? In order to shed light on these questions, we outline a very complete strategy by using different techniques of vibrational spectroscopy sensitive (VCD) and not sensitive (IR, FarIR and Raman) to the chirality together with quantum chemical calculations.
Supramolecular organization of perfluorinated 1H-indazoles in the solid state using X-ray crystallography, SSNMR and sensitive (VCD) and non sensitive (MIR, FIR and Raman) to chirality vibrational spectroscopies
(Royal Society of Chemistry, 2017) Quesada-Moreno, María del Mar; Avilés-Moreno, Juan Ramón; López-González, Juan Jesús; Jacob, Kane; Vendier, Laure; Etienne, Michel; Alkorta, Ibon; Elguero, José; Claramunt, Rosa M.
1H-Indazole derivatives exhibit a remarkable property since some of them form chiral supramolecular structures starting from achiral monomers. The present work deals with the study of three perfluorinated 1H-indazoles that resolve spontaneously as conglomerates. These conglomerates can contain either a pure enantiomer (one helix) or a mixture of both enantiomers (both helices) with an enantiomeric excess (e.e.) of one of them. The difficulty of the structural analysis of these types of compounds is thus clear. We outline a complete strategy to determine the structures and configurations (M or P helices) of the enantiomers (helices) forming the conglomerates of these perfluorinated 1H-indazoles based on X-ray crystallography, solid state NMR spectroscopy and different solid state vibrational spectroscopies that are either sensitive (VCD) or not (FarIR, IR and Raman) to chirality, together with quantum chemical calculations (DFT).
Ultrasound-assisted surfactant-enhanced emulsification microextraction for the determination of carbamates in wines by ultra-high performance liquid chromatography–tandem mass spectrometry
(Elsevier, 2013) Moreno-González, David; Huertas-Pérez, José F.; García-Campaña, Ana M.; Gámiz-Gracia, Laura
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 μg l−1, showing the high sensitivity of this fast and simple method and its compliance with current requirements.
Understanding the Aldo-Enediolate Tautomerism of Glycolaldehyde in Basic Aqueous Solutions
(Wiley, 2015) Azofra, Luis Miguel; Quesada-Moreno, María del Mar; Alkorta, Ibon; Avilés-Moreno, Juan Ramón; Elguero, José; López-González, Juan Jesús
The biochemically important interconversion process between aldoses and ketoses is assumed to take place via 1,2-enediol or 1,2-enediolate intermediates, but such intermediates have never been isolated. The current work was undertaken in an attempt to detect the presence of the 1,2-enediol structure of glycolaldehyde in alkaline medium, actually a 1,2-enediolate, and to try to clarify the scarce data existing about both the formation of the deprotonated enediol and the aldo-enediolate equilibrium. The Raman spectra of neutral and basic solutions were recorded as a function of time for eleven days. Several bands associated with the presence of the enediolate were observed in alkaline medium. Glycolaldehyde exists as three different structures in aqueous solution at neutral pH, i.e. hydrated aldehydes, aldehydes and dimers, with a respective ratio of approximately 4:0.25:1. Additionally, the formation of Z-enediolate forms takes place at basic pH, together with the increase of aldehyde species, as 2-oxoethan-1-olate, and the decrease of hydrated aldehyde and dimeric forms. The theoretical ratio ~1.5:1 aldehyde:Z-enediolate reproduces the experimental Raman spectrum in basic medium, with the additional contribution of the previously mentioned ratio between hydrated aldehyde and dimeric forms. Finally, Raman spectroscopy allowed us to monitor the enolization of this carbohydrate model and to conclude that the aldo-enediol tautomerism, formally aldo-enediolate, happens when a suitable amount of basic species is added.

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