Direct analysis of olive oil and other vegetable oils by mass spectrometry: a review

Virgin olive oil (VOO) is a highly valued vegetable oil often subjected to fraud practices such as adulteration with lower prized oils such as seed oils and refined olive oil. Thus, there is a need to provide rapid tools that allow high-throughput authentication and quality control of VOO as well as other valued oils. Mass spectrometry offers unique features -such as specificity, sensitivity and speed of analysis-that map well against this challenge, either those based on atmospheric pressure ionization methods (ESI and APCI) or those occurring under vacuum conditions such as MALDI for nonvolatile species or headspace sampling-mass spectrometry using electron impact ionization (HS-MS) or chemical ionization (proton transfer reaction mass spectrometry (PTR-MS) and selected ion flow tube mass spectrometry (SIFT-MS)) for volatile fraction analysis. In addition, more recent atmospheric pressure methods (Ambient MS) enable direct analysis with minor or even no sample manipulation. The aim of this article is to provide a critical overview on all these methods and their potential use for vegetable oil characterization, highlighting the strengths and weaknesses of the differentMarie Sklodowska-Curie (MSCA) grant agreement number 840743, EU FEDER funds and the Research Programme of the University of Jaen (Plan 2019–2020, Research programme “Acción 10”) and Regional Government of Andalucía, Spain (Project Ref. PY2018-1211)

Comprehensive and heart-cutting multidimensional liquid chromatography–mass spectrometry and its applications in food analysis

In food analysis, conventional one‐dimensional liquid chromatography methods sometimes lack sufficient separation power due to the complexity and heterogeneity of the analyzed matrices. Therefore, the use of two‐dimensional liquid chromatography (2D‐LC) turns out to be a powerful tool to consider, especially when coupled to mass spectrometry (MS). This review presents the most remarkable 2D‐LC–MS food applications reported in the last 10 years, including a critical discussion of the multiple approaches, modulation strategies as well as the importance of the optimization of the different analytical aspects that will condition the 2D‐LC–MS performance. The presence of contaminants in food (food safety), the food quality, and authenticity or the relationship between the beneficial effects of food and human health are some of the fields in which most of the 2D‐LC–MS applications are mainly focused. Both heart‐cutting and comprehensive applications are described and discussed in this review, highlighting the potential of 2D‐LC–MS for the analysis of such complex samples.Consejería de Economía, Conocimiento, Empresas y Universidad, Junta de Andalucía (Project Ref. PY2018‐1211, partially supported by EU FEDER funds; postdoctoral research fellowship ref. DOC_01319). Agencia Estatal de Investigación (AEI) y Ministerio de Ciencia MCIN/AEI/10.13039/501100011033 (MACFRAUD project ref. PID2021‐123307OB‐I00; FPU20/02933; Ramón y Cajal RYC2019‐026581‐I y RYC2021‐033148‐I)

Ambient Diode Laser Desorption Dielectric Barrier Discharge Ionization Mass Spectrometry of Nonvolatile Chemicals

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.The financial support by the “Ministerium für Innovation, Wissenschaft und Forschung des Landes Nordrhein-Westfalen” and by the “Bundesministerium für Bildung und Forschung” is gratefully acknowledged. The authors also acknowledge funding support from Regional Government of Andalusia (Spain) “Junta de Andalucía” (Project Ref. P07-FQM-2614 and AGR-6066) and the Spanish “Ministerio de Economía y Competitividad” (No. CTQ-2012-34297). B.G.-L. also acknowledges a scholarship from the German Academic Exchange Service (Postdoctoral Leibniz-DAAD program (PKZ: A/11/94543))

Downstream processing of Isochrysis galbana: a step towards microalgal biorefinery

An algae-based biorefinery relies on the efficient use of algae biomass through its fractionation of several valuable/bioactive compounds that can be used in industry. If this biorefinery includes green platforms as downstream processing technologies able to fulfill the requirements of green chemistry, it will end-up with sustainable processes. In the present study, a downstream processing platform has been developed to extract bioactive compounds from the microalga Isochrysis galbana using various pressurized green solvents. Extractions were performed in four sequential steps using (1) supercritical CO2 (ScCO2), (2) ScCO2/ethanol (Gas Expanded Liquid, GXL), (3) pure ethanol, and (4) pure water as solvents, respectively. The residue of the extraction step was used as the raw material for the next extraction. Optimization of the ScCO2 extraction was performed by factorial design in order to maximize carotenoid extraction. During the second step, different percentages of ethanol were evaluated (15%, 45% and 75%) in order to maximize the extraction yield of fucoxanthin, the main carotenoid present in this alga; the extraction of polar lipids was also an aim. The third and fourth steps were performed with the objective of recovering fractions with high antioxidant activity, eventually rich in carbohydrates and proteins. The green downstream platform developed in this study produced different extracts with potential for application in the food, pharmaceutical and cosmetic industries. Therefore, a good approach for complete revalorization of the microalgae biomass is proposed, by using processes complying with the green chemistry principlesThe authors acknowledge funding from the EU MIRACLES project (7th Framework Program - Grant Agreement No. 613588). B.G.L. thanks MINECO (Ministerio de Economía y Competitividad) for her Juan de la Cierva postdoctoral research contract. M.H. thanks MINECO for his Ramón y Cajal postdoctoral research contract

Nuevas metodologías analíticas basadas en espectrometrías de masas para el análisis multi-residuo de plaguicidas y otros contaminantes en vegetales con alto contenido graso y en productos alimenticios de origen vegetal

Tesis Univ. Jaén. Departamento de Química Física y Analítica. Leída el 17 de diciembre de 201

Diseño experimental para la extracción de los polifenoles de las bayas de goji diferentes por extracción líquido a presión

Resumen del póster presentado a las II Jornadas Científicas CIAL-Fórum, celebradas durante los dias 16 y 17 de noviembre de 2016 en el Instituto de Investigación en Ciencias de la Alimentación (CIAL).En los últimos años, las bayas de Goji (Lycium barbarum L.) han generado un gran interés debido sus efectos beneficiosos para la salud humana, tales como actividad antioxidante, anti-inflamatoria y antitumoral, los cuales se han atribuido a los polifenoles presentes en el fruto. La extracción de compuestos fenólicos de las bayas de Goji ha sido poco estudiada: algunos estudios se han enfocado a su optimización mediante técnicas convencionales, pero la extracción de compuestos fenólicos utilizando la técnica de líquidos presurizados (PLE) no se ha empleado anteriormente para las bayas Goji. Por lo anterior, este trabajo tuvo como objetivo la optimización de la extracción de compuestos fenólicos de bayas de Goji con PLE mediante un diseño experimental basado en la metodología de superficie multi-respuesta (MSR). Se han evaluado cuatro muestras de bayas de Goji: fruta comercial y tres especies cultivadas: Polonia, Selvatico mongolo y Bigol. Se aplicó un diseño experimental factorial de tres niveles (3^2) para estudiar el efecto de la temperatura (50-180 °C) y el porcentaje de etanol (0-100%) en el rendimiento de extracción, el contenido de fenoles totales (CFT), flavonoides totales (FT) y la capacidad antioxidante equivalente de Trolox (TEAC) como variables de respuesta. Las condiciones óptimas predichas para la extracción fueron 180 °C y 86% de etanol con un rendimiento del 70%, CFT= 62,2 mg EAG/ g extracto, FT = 3,2 mg de quercetina/ g extracto y TEAC = 0,7 mmol Eq Trolox/ g extracto como respuestas óptimas predichas para la muestra comercial. Posteriormente, se evaluarán las condiciones óptimas de extracción en las cuatro muestras de baya Goji para observar diferencias. Además, se hará la caracterización de los polifenoles presentes en cada una de las variedades de las bayas Goji empleando HPLC-DAD-MS/MS.G. Tripodo agradece al Ministerio de Educación y a la Università Campus Bio-Medico, Unidad de ciencias de la alimentación y la nutrición, Roma, Italia por su apoyo financiero para la realización de su estancia doctoral.Peer reviewe

Green foodomics. Towards a cleaner scientific discipline

In the present review, we have tried to highlight foodomics' goals with regards to green chemistry principles providing an update (from mid-2013 up to 2017) on the novelties and new approaches that can be employed to make foodomics greener. Although Foodomics covers different fields of research included in food science approached using advanced -omics technologies and associated to sustainability, in the present work only those directly related to green analytical chemistry (GAC) and novel foods development are discussed. Aspects treated in the present work deal with new trends in production of functional food ingredients (through the use of alternative solvents and design of biorefinery processes) and with green alternatives mainly for metabolomics and proteomics. Moreover, different methodologies to quantify the greenness of the processes are presented.The present work was supported by the projects AGL2014-53609-P (Ministerio de Economía y Competitividad, Spain), S2013/ABI-2728 (Comunidad de Madrid), I-LINK1096 (CSIC) and MIRACLES EU project (7th Framework Program – Grant Agreement No. 613588). B.G.L. thanks MINECO (Ministerio de Economía y Competitividad) of Spain for her Juan de la Cierva postdoctoral research contract (ref. JCI-2012-12972).Peer reviewe

Evaluation of different cleanup sorbents for multiresidue pesticide analysis in fatty vegetable matrices by liquid chromatography tandem mass spectrometry

In this article we have evaluated the performance of different sorbents for the cleanup step in multiresidue pesticide analysis in fatty vegetable matrices using QuEChERS methodology. The three different matrices tested (olive oil, olives and avocado) were partitioned using acetonitrile prior to cleanup step. Afterwards, the supernatant was purified using different sorbents: C18+PSA (primary secondary amine), Z-Sep (zirconium oxide and C18 dual bonded to silica), Z-Sep (zirconium oxide bonded to silica) and a novel sorbent Enhanced Matrix Removal-Lipid (EMR) whose composition has not been disclosed. The different cleanup strategies were compared for a group of 67 representative pesticides in terms of recovery rates, matrix effects, extract cleanliness and precision using ultra-high performance liquid chromatography tandem mass spectrometry (UHPLC–MS/MS). The best extraction efficiencies in olive oil matrix were obtained using EMR, while the results for olives and avocado were pretty similar amongst the different sorbents with an overall lower performance in terms of matrix effects and recovery rates compared to olive oil data, particularly in olives due to the higher complexity and concentration of coextracted species. On the other hand, the average reproducibility was clearly better when EMR sorbent was employed in all selected matrices for most pesticides (RSD < 10% for 45, 52, and 56 pesticides in avocado, olives and olive oil respectively). The best results in terms of matrix effects were also obtained with EMR; with signal suppression lower than 20% for 79%, 16% and 51% of pesticides tested in olive oil, olives and avocado respectively. Using EMR as cleanup sorbent, limits of quantitation using UHPLC–MS/MS, ranged from 0.10 to 90 μg kg, allowing their determination at the low concentration levels demanded by current olive oil regulations in most cases.The authors acknowledge funding support from the Regional Government of Andalusia (Spain), Junta de Andalucía (Projects AGR-6066, AGR-6182 and Research Group FQM-323). D.M.G. thanks the Spanish Ministerio de Economía y Competitividad (MINECO) for a Juan de la Cierva postdoctoral contract. J.R.M. acknowledges funding from Plan Propio de Investigacion of Universidad de Jaén (Ref. 2015/00018/001). B.G.L. acknowledges MINECO for her Juan de la Cierva postdoctoral research contract (ref. JCI-2012-12972).Peer Reviewe

Phytochemical composition of Ecballium elaterium extracts with antioxidant and anti-inflammatory activities: Comparison among leaves, flowers and fruits extracts

Ecballium elaterium (squirting cucumber) is a Mediterranean plant used in folk medicine. Especially fruits and fruits juice are administered for several therapeutic uses, although they can be toxic at high doses. In the present work, a phytochemical characterization of different parts of the plant, namely fruits, flowers and leaves, was made. Extracts were analyzed by liquid chromatography coupled to diode array detector and mass spectrometry with triple quadrupole analyzer (HPLC-DAD-MS/MS). Only one cucurbitacin, Cuc D, was found in the three extracts, and an additional one, Cuc P, was tentatively identified for the first time in fruits extract. Additionally, several flavonoids such as rutin, narcissin and kaempferol were tentatively identified in the plant. Antioxidant activity was evaluated by DPPH, ABTS, FRAP and inhibition of human erythrocyte hemolysis mediated by AAPH. Results revealed that flowers extract was the most active one, with an EC50 of 46.01 µg/ml for DPPH and TEAC values of 489.11 and 160.97 µmol Trolox/g extract for ABTS and FRAP respectively; despite the protective effect of all extracts in AAPH assay was relatively moderated. In case of anti-inflammatory activity, all extracts were active by inhibiting heat induced protein denaturation in a non-dose dependent manner, showed protection against hypotonic hemolysis and reduction of mice hind paw edema, 3 h after carrageenan injection; as for previous tests, flowers extract exhibited the highest percentage of inhibition (82.93%) of hind paw edema at a dose of 200 mg/kg. Therefore, E. Elaterium flowers extract showed potential antioxidant and anti-inflammatory effects similar to those exerted by the fruits.L.B. would like to thank the University of Bejaia for the grant of fellowship that enabled the realization of part of this work in the laboratory of Foodomics in Madrid (Spain). B.G.L. thanks Spanish Ministerio de Economía y Competitividad for her Juan de la Cierva postdoctoral research contract.Peer reviewe

A feasibility study of UHPLC-HRMS accurate-mass screening methods for multiclass testing of organic contaminants in food

The feasibility of accurate-mass multi-residue screening methods using liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS) using time-of-flight mass spectrometry has been evaluated, including over 625 multiclass food contaminants as case study. Aspects such as the selectivity and confirmation capability provided by HRMS with different acquisition modes (full-scan or full-scan combined with collision induced dissociation (CID) with no precursor ion isolation), and chromatographic separation along with main limitations such as sensitivity or automated data processing have been examined. Compound identification was accomplished with retention time matching and accurate mass measurements of the targeted ions for each analyte (mainly (de)protonated molecules). Compounds with the same nominal mass (isobaric species) were very frequent due to the large number of compounds included. Although 76% of database compounds were involved in isobaric groups, they were resolved in most cases (99% of these isobaric species were distinguished by retention time, resolving power, isotopic profile or fragment ions). Only three pairs could not be resolved with these tools. In-source CID fragmentation was evaluated in depth, although the results obtained in terms of information provided were not as thorough as those obtained using fragmentation experiments without precursor ion isolation (all ion mode). The latter acquisition mode was found to be the best suited for this type of large-scale screening method instead of classic product ion scan, as provided excellent fragmentation information for confirmatory purposes for an unlimited number of compounds. Leaving aside the sample treatment limitations, the main weaknesses noticed are basically the relatively low sensitivity for compounds which does not map well against electrospray ionization and also quantitation issues such as those produced by signal suppression due to either matrix effects from coeluting matrix or from coeluting analytes present in the standards solutions which often occur as they contain hundreds of the analytes included in the screening methods.The authors acknowledge funding from the Spanish Ministerio de Economía y Competitividad (MINECO) (Refs. CTQ-2009-10897 and CTQ-2012-34297). P.P.-O acknowledges a PhD scholarship from University of Jaén. F.J.L.-O. acknowledges a PhD student scholarship from MINECO (Ref. BES-2013-064014).Peer Reviewe