Unravelling the Distribution of Secondary Metabolites in Olea europaea L.: Exhaustive Characterization of Eight Olive-Tree Derived Matrices by Complementary Platforms (LC-ESI/APCI-MS and GC-APCI-MS)

In order to understand the distribution of the main secondary metabolites found in Olea europaea L., eight different samples (olive leaf, stem, seed, fruit skin and pulp, as well as virgin olive oil, olive oil obtained from stoned and dehydrated fruits and olive seed oil) coming from a Picudo cv. olive tree were analyzed. All the experimental conditions were selected so as to assure the maximum coverage of the metabolome of the samples under study within a single run. The use of LC and GC with high resolution MS (through different ionization sources, ESI and APCI) and the annotation strategies within MetaboScape 3.0 software allowed the identification of around 150 compounds in the profiles, showing great complementarity between the evaluated methodologies. The identified metabolites belonged to different chemical classes: triterpenic acids and dialcohols, tocopherols, sterols, free fatty acids, and several sub-types of phenolic compounds. The suitability of each platform and polarity (negative and positive) to determine each family of metabolites was evaluated in-depth, finding, for instance, that LC-ESI-MS (+) was the most efficient choice to ionize phenolic acids, secoiridoids, flavonoids and lignans and LC-APCI-MS was very appropriate for pentacyclic triterpenic acids (MS (−)) and sterols and tocopherols (MS (+)). Afterwards, a semi-quantitative comparison of the selected matrices was carried out, establishing their typical features (e.g., fruit skin was pointed out as the matrix with the highest relative amounts of phenolic acids, triterpenic compounds and hydroxylated fatty acids, and seed oil was distinctive for its high relative levels of acetoxypinoresinol and tocopherols).

[1]  A. Fernandez-Gutiérrez,et al.  Exploring the Capability of LC‐MS and GC‐MS Multi‐Class Methods to Discriminate Virgin Olive Oils from Different Geographical Indications and to Identify Potential Origin Markers , 2019, European Journal of Lipid Science and Technology.

[2]  A. Fernandez-Gutiérrez,et al.  Deep insight into the minor fraction of virgin olive oil by using LC-MS and GC-MS multi-class methodologies. , 2018, Food chemistry.

[3]  P. Domingues,et al.  Olive (Olea europaea L. cv. Galega vulgar) Seed Oil: A First Insight into the Major Lipid Composition of a Promising Agro‐Industrial By‐Product at Two Ripeness Stages , 2018 .

[4]  S. Sahin,et al.  Olive tree (Olea europaea L.) leaf as a waste by-product of table olive and olive oil industry: a review. , 2018, Journal of the science of food and agriculture.

[5]  E. Medina,et al.  New by-products rich in bioactive substances from the olive oil mill processing. , 2018, Journal of the science of food and agriculture.

[6]  E. Perri,et al.  Integrated approach for the eco design of a new process through the life cycle analysis of olive oil: Total use of olive by-products , 2017 .

[7]  Z. Jianguo,et al.  Metabolomics reveals variation and correlation among different tissues of olive (Olea europaea L.) , 2017, Biology Open.

[8]  A. Segura‐Carretero,et al.  RP-HPLC-DAD-ESI-QTOF-MS based metabolic profiling of the potential Olea europaea by-product "wood" and its comparison with leaf counterpart. , 2017, Phytochemical analysis : PCA.

[9]  J. Lozano-Sánchez,et al.  AMPK modulatory activity of olive–tree leaves phenolic compounds: Bioassay-guided isolation on adipocyte model and in silico approach , 2017, PloS one.

[10]  A. Albini,et al.  Nutrigenomics of extra‐virgin olive oil: A review , 2017, BioFactors.

[11]  Yu Bai,et al.  Online coupling techniques in ambient mass spectrometry. , 2016, The Analyst.

[12]  F. Schena,et al.  Robustness of NMR-based metabolomics to generate comparable data sets for olive oil cultivar classification. An inter-laboratory study on Apulian olive oils. , 2016, Food chemistry.

[13]  Rosaria Ciriminna,et al.  Extraction, benefits and valorization of olive polyphenols , 2016 .

[14]  A. Fernandez-Gutiérrez,et al.  Evaluating the potential of LC coupled to three alternative detection systems (ESI-IT, APCI-TOF and DAD) for the targeted determination of triterpenic acids and dialcohols in olive tissues. , 2016, Talanta.

[15]  A. Gómez-Caravaca,et al.  From Olive Fruits to Olive Oil: Phenolic Compound Transfer in Six Different Olive Cultivars Grown under the Same Agronomical Conditions , 2016, International journal of molecular sciences.

[16]  Emma L. Schymanski,et al.  MetFrag relaunched: incorporating strategies beyond in silico fragmentation , 2016, Journal of Cheminformatics.

[17]  A. Varela-López,et al.  Olive Oil and the Hallmarks of Aging , 2016, Molecules.

[18]  A. Fernandez-Gutiérrez,et al.  Comparing two metabolic profiling approaches (liquid chromatography and gas chromatography coupled to mass spectrometry) for extra-virgin olive oil phenolic compounds analysis: A botanical classification perspective. , 2016, Journal of chromatography. A.

[19]  M. Özcan,et al.  A review: benefit and bioactive properties of olive (Olea europaea L.) leaves , 2016, European Food Research and Technology.

[20]  M. Servili,et al.  Metabolomics of Olive Fruit: A Focus on the Secondary Metabolites , 2016 .

[21]  J. Saraiva,et al.  Emerging opportunities for the effective valorization of wastes and by-products generated during olive oil production process: Non-conventional methods for the recovery of high-added value compounds , 2015 .

[22]  Fernando J. Reyes-Zurita,et al.  Anti-cancer and Anti-angiogenic Properties of Various Natural Pentacyclic Tri-terpenoids and Some of their Chemical Derivatives , 2015 .

[23]  I. Boldizsár,et al.  Phenolic profiling of various olive bark-types and leaves: HPLC–ESI/MS study , 2015 .

[24]  S. Jafari,et al.  Bioactive profile, dehydration, extraction and application of the bioactive components of olive leaves , 2015 .

[25]  A. Skaltsounis,et al.  UHPLC-DAD-FLD and UHPLC-HRMS/MS based metabolic profiling and characterization of different Olea europaea organs of Koroneiki and Chetoui varieties § , 2015 .

[26]  Muhammad Ali Hashmi,et al.  Traditional Uses, Phytochemistry, and Pharmacology of Olea europaea (Olive) , 2015, Evidence-based complementary and alternative medicine : eCAM.

[27]  A. Skaltsounis,et al.  From Drupes to Olive Oil: An Exploration of Olive Key Metabolites , 2015 .

[28]  M. Fitó,et al.  Minor Bioactive Olive Oil Components and Health: Key Data for Their Role in Providing Health Benefits in Humans , 2015 .

[29]  M. D. L. Castro.  Towards a comprehensive exploitation of agrofood residues: Olive tree – olive oil as example , 2014 .

[30]  G. Beltrán,et al.  Bioactive properties of the main triterpenes found in olives, virgin olive oil, and leaves of Olea europaea. , 2013, Journal of agricultural and food chemistry.

[31]  A. Fernandez-Gutiérrez,et al.  Evaluation of gas chromatography-atmospheric pressure chemical ionization-mass spectrometry as an alternative to gas chromatography-electron ionization-mass spectrometry: avocado fruit as example. , 2013, Journal of chromatography. A.

[32]  M. Nadour,et al.  Olive mill wastes: Biochemical characterizations and valorization strategies , 2013 .

[33]  A. Skaltsounis,et al.  From Olive Drupes to Olive Oil. An HPLC-Orbitrap-based Qualitative and Quantitative Exploration of Olive Key Metabolites , 2013, Planta Medica.

[34]  W. Hurst,et al.  Quantitative Analysis of Phytosterols in Edible Oils Using APCI Liquid Chromatography–Tandem Mass Spectrometry , 2013, Lipids.

[35]  J. Lozano-Sánchez,et al.  Literature review on production process to obtain extra virgin olive oil enriched in bioactive compounds. Potential use of byproducts as alternative sources of polyphenols. , 2013, Journal of agricultural and food chemistry.

[36]  G. Besnard,et al.  Primary domestication and early uses of the emblematic olive tree: palaeobotanical, historical and molecular evidence from the Middle East , 2012, Biological reviews of the Cambridge Philosophical Society.

[37]  Farooq Anwar,et al.  Valuable Nutrients and Functional Bioactives in Different Parts of Olive (Olea europaea L.)—A Review , 2012, International journal of molecular sciences.

[38]  Hanaâ Zbakh,et al.  Potential use of olive mill wastewater in the preparation of functional beverages: A review , 2012 .

[39]  Y. Orihara,et al.  Biosynthesis of acteoside in cultured cells of Olea europaea , 2010, Journal of Natural Medicines.

[40]  Matthias Müller-Hannemann,et al.  In silico fragmentation for computer assisted identification of metabolite mass spectra , 2010, BMC Bioinformatics.

[41]  A. Segura‐Carretero,et al.  Multi-component analysis (sterols, tocopherols and triterpenic dialcohols) of the unsaponifiable fraction of vegetable oils by liquid chromatography-atmospheric pressure chemical ionization-ion trap mass spectrometry. , 2009, Talanta.

[42]  E. Simó-Alfonso,et al.  Classification of extra virgin olive oils produced at La Comunitat Valenciana according to their genetic variety using sterol profiles established by high-performance liquid chromatography with mass spectrometry detection. , 2009, Journal of agricultural and food chemistry.

[43]  M. Servili,et al.  Biosynthesis and biotransformations of phenol-conjugated oleosidic secoiridoids from Olea europaea L. , 2008, Natural product reports.

[44]  Ana Jiménez,et al.  Olive stone an attractive source of bioactive and valuable compounds. , 2008, Bioresource technology.

[45]  D. Bedgood,et al.  Chemical screening of olive biophenol extracts by hyphenated liquid chromatography. , 2007, Analytica chimica acta.

[46]  Paul Vossen,et al.  Olive Oil: History, Production, and Characteristics of the World's Classic Oils , 2007 .

[47]  A. Kamal-Eldin,et al.  Comparison of reversed-phase liquid chromatography-mass spectrometry with electrospray and atmospheric pressure chemical ionization for analysis of dietary tocopherols. , 2007, Journal of chromatography. A.

[48]  A. Fernandez-Gutiérrez,et al.  Separation and determination of sterols in olive oil by HPLC-MS , 2007 .

[49]  Rafael Borja,et al.  Treatment technologies of liquid and solid wastes from two-phase olive oil mills , 2006 .

[50]  D. Kell,et al.  Metabolic profiling using direct infusion electrospray ionisation mass spectrometry for the characterisation of olive oils. , 2002, The Analyst.

[51]  D. Caruso,et al.  Rapid evaluation of phenolic component profile and analysis of oleuropein aglycon in olive oil by atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). , 2000, Journal of agricultural and food chemistry.

[52]  Maurizio Servili,et al.  High-performance liquid chromatography evaluation of phenols in olive fruit, virgin olive oil, vegetation waters, and pomace and 1D- and 2D-nuclear magnetic resonance characterization , 1999 .

[53]  M. Servili,et al.  Phenolic compounds of olive fruit: one- and two-dimensional nuclear magnetic resonance characterization of Nüzhenide and its distribution in the constitutive parts of fruit. , 1999, Journal of agricultural and food chemistry.

[54]  Valentina Ruiz-Gutiérrez,et al.  Glucósidos fenólicos amargos de las semillas del olivo (Olea europea) , 1994 .

[55]  D. Schwartz,et al.  The formation of oxo- and hydroxy-fatty acids in heated fats and oils , 1994 .