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Oxidized Forms of Olive Oil Secoiridoids: Semisynthesis, Identification and Correlation with Quality Parameters[ # ]Supported by: European Regional Development Fund (ERDF) and Greek national funds through the Operational Program "Competitiveness, Entrepreneurship and Innovation", under the call “RESEARCH – CREATE - INNOVATE” (project HOLEA code: 03816)
Supported by: European Union and project OliveNet-H2020-MSCA-RISE-2016 – “Bioactive compounds from Olea europaea: investigation and application in food, cosmetic and pharmaceutical industry” (Proposal Number: 734899) under the Horizon2020 framework
Supported by: European Union (ERDF) and Greek national funds through the Operational Program "Competitiveness, Entrepreneurship and Innovation", under the call “Strengthening research and Innovation Infrastructures” (Plant Up, project code:5002803)
Secoiridoids is the prominent chemical class of olive oil polar constituents and are characterized by significant biological properties. They are abundant in different chemical forms and relatively high concentrations compared to other components, while prone to oxidation due to their chemical motif. In recent years, oxidized derivatives of secoiridoids have been reported, either as natural constituents of olive oil or as components which are gradually formed in all stages of its production and storage. The mono-oxidized forms of oleocanthal and oleacein named as the respective acids have been recently isolated from olive oil and unambiguously structurally characterized. Other oxidized forms of elenolic acid or more complex secoiridoids, such as those of oleuropein and ligstroside aglycones are also sporadically mentioned in the literature. No further information is provided since they have not been isolated in pure form in order to be accurately identified. Most of the time, they are generally referred as oxidized forms of the parent compounds and commonly identified based on mass spectrometric data. In the current study, the semi-synthesis of the main oxidized olive oil secoiridoids, i.e., oleocanthalic acid, oleaceinic acid, EDA acid, carboxylic form of elenolic acid, carboxylic form of ligstroside aglycon, and carboxylic form of oleuropein aglycon is described starting from the corresponding aldehydic derivatives, using SeO2/H2O2 as oxidative agents. Furthermore, their presence in a number of Greek olive oils was investigated as well, as possible correlation thereof with quality parameters.
Key wordsOxidized Secoiridoid Compounds - Oleocanthal - Oleocanthalic acid - Semi-synthesis - Olive oil - Quality parameters - Olea europaea - Oleaceae
# Dedicated to Professor Dr. A. Douglas Kinghorn on the occasion of his 75th birthday.
Received: 25 November 2021
Accepted after revision: 01 February 2022
Accepted Manuscript online:
23 March 2022
Article published online:
01 July 2022
© 2022. The Author(s). This is an open access article published by Thieme under the terms of the Creative Commons Attribution-NonDerivative-NonCommercial License, permitting copying and reproduction so long as the original work is given appropriate credit. Contents may not be used for commecial purposes, or adapted, remixed, transformed or built upon. (https://creativecommons.org/licenses/by-nc-nd/4.0/)
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- 1 Owen RW, Giacosa A, Hull WE, Haubner R, Würtele G, Spiegelhalder B, Bartsch H. Olive-oil consumption and health: the possible role of antioxidants. Lancet Oncol 2000; 1: 107-112
- 2 Dais P, Hatzakis E. Quality assessment and authentication of virgin olive oil by NMR spectroscopy: A critical review. Anal Chim Acta 2013; 765: 1-27 DOI: 10.1016/j.aca.2012.12.003.
- 3 Ray NB, Hilsabeck KD, Karagiannis TC, McCord DE. Bioactive Olive Oil Polyphenols in the Promotion of Health. In: Singh RB, Watson RR, Takahashi T. eds. The Role of Functional Food Security in Global Health. Oxford: Elsevier Inc.; 2019: 623-637
- 4 Covas MI, Fitó M, De La Torre R. Minor bioactive olive oil components and health: Key data for their role in providing health benefits in humans. AOCS Press 2015; 2015: 31-52 DOI: 10.1016/B978-1-63067-041-2.50008-2.
- 5 Boskou D, Blekas G, Tsimidou M. Olive Oil Composition. Boskou D, ed. Olive Oil (Second Edition). Oxford: Elsevier Inc.; 2006: 41-72
- 6 Bianco A, Coccioli F, Guiso M, Marra C. The occurrence in olive oil of a new class of phenolic compounds: hydroxy-isochromans. Food Chem 2002; 77: 405-411
- 7 European Food Safety Authority (EFSA). Scientific Opinion. ESFA J 2011; 9: 2033-2058
- 8 De La Torre-Carbot K, Jauregui O, Gimeno E, Castellote AI, Lamuela-Raventós RM, López-Sabater MC. Characterization and quantification of phenolic compounds in olive oils by solid-phase extraction, HPLC-DAD, and HPLC-MS/MS. J Agric Food Chem 2005; 53: 4331-4340
- 9 Vichi S, Cortés-Francisco N, Caixach J. Insight into virgin olive oil secoiridoids characterization by high-resolution mass spectrometry and accurate mass measurements. J Chromatogr A 2013; 1301: 48-59 DOI: 10.1016/j.chroma.2013.05.047.
- 10 Bongiorno D, Di Stefano V, Indelicato S, Avellone G, Ceraulo L. Bio-phenols determination in olive oils: Recent mass spectrometry approaches. Mass Spectrom Rev 2021; e21744 DOI: 10.1002/mas.21744.
- 11 Nikou T, Witt M, Stathopoulos P, Barsch A, Halabalaki M. Olive oil quality and authenticity assessment aspects employing FIA-MRMS and LC-Orbitrap MS Metabolomic Approaches. Front Public Health 2020; 8: 558226
- 12 Kotsiou K, Tasioula-Margari M. Monitoring the phenolic compounds of Greek extra-virgin olive oils during storage. Food Chem 2016; 200: 255-262
- 13 International Olive Council. Determination of Biophenols in Olive Oils by HPLC. COI/T20/Doc No 29/Rev1 2017; 29: 1-8
- 14 García-Villalba R, Carrasco-Pancorbo A, Oliveras-Ferraros C, Vázquez-Martín A, Menéndez JA, Segura-Carretero A, Fernández-Gutiérrez A. Characterization and quantification of phenolic compounds of extra-virgin olive oils with anticancer properties by a rapid and resolutive LC-ESI-TOF MS method. J Pharm Biomed Anal 2010; 51: 416-429
- 15 Daskalaki D, Kefi G, Kotsiou K, Tasioula-Margari M. Evaluation of phenolic compounds degradation in virgin olive oil during storage and heating. J Food Nutr Res (Slovak Republic) 2009; 48: 31-41
- 16 Lozano-Sánchez J, Castro-Puyana M, Mendiola JA, Segura-Carretero A, Cifuentes A, Ibáñez E. Recovering bioactive compounds from olive oil filter cake by advanced extraction techniques. Int J Mol Sci 2014; 15: 16270-16283
- 17 Lozano-Sánchez J, Giambanelli E, Quirantes-Piné R, Cerretani L, Bendini A, Segura-Carretero A, Fernández-Gutiérrez A. Wastes generated during the storage of extra virgin olive oil as a natural source of phenolic compounds. J Agric Food Chem 2011; 59: 11491-11500
- 18 Farré M, Picó Y, Barceló D. Direct analysis in real-time high-resolution mass spectrometry as a valuable tool for polyphenols profiling in olive oil. Anal Methods 2019; 11: 472-482 DOI: 10.1039/C8AY01865K.
- 19 Angelis A, Antoniadi L, Stathopoulos P, Halabalaki M, Skaltsounis LA. Oleocanthalic and Oleaceinic acids: New compounds from Extra Virgin Olive Oil (EVOO). Phytochem Lett 2018; 26: 190-194 DOI: 10.1016/j.phytol.2018.06.020.
- 20 De Ceglie C, Abbattista R, Losito I, Castellaneta A, Calvano CD, Bianco G, Palmisano F, Cataldi TRI. Influence of horizontal centrifugation processes on the content of phenolic secoiridoids and their oxidized derivatives in commercial olive oils: An insight by liquid chromatography-high-resolution mass spectrometry and chemometrics. J Agric Food Chem 2020; 68: 3171-3183
- 21 Abbattista R, Losito I, Castellaneta A, De Ceglie C, Calvano CD, Cataldi TRI. Insight into the storage-related oxidative/hydrolytic degradation of olive oil secoiridoids by liquid chromatography and high-resolution fourier transform mass spectrometry. J Agric Food Chem 2020; 68: 12310-12325
- 22 Castillo-Luna A, Criado-Navarro I, Ledesma-Escobar CA, López-Bascón MA, Priego-Capote F. The decrease in the health benefits of extra virgin olive oil during storage is conditioned by the initial phenolic profile. Food Chem 2021; 336: 127730 DOI: 10.1016/j.foodchem.2020.127730.
- 23 Angelis A, Michailidis D, Antoniadi L, Stathopoulos P, Tsantila V, Nuzillard JM, Renault JH, Skaltsounis LA. Pilot continuous centrifugal liquid-liquid extraction of extra virgin olive oil biophenols and gram-scale recovery of pure oleocanthal, oleacein, MFOA, MFLA and hydroxytyrosol. Sep Purif Technol 2021; 255: 117692
- 24 Angelis A, Hamzaoui M, Aligiannis N, Nikou T, Michailidis D, Gerolimatos P, Termentzi A, Hubert J, Halabalaki M, Renault JH, Skaltsounis AL. An integrated process for the recovery of high added-value compounds from olive oil using solid support free liquid-liquid extraction and chromatography techniques. J Chromatogr A 2017; 1491: 126-136
- 25 Dai PF, Qu JP, Kang YB. Organocatalyzed aerobic oxidation of aldehydes to acids. Org Lett 2019; 21: 1393-1396
- 26 Gaspa S, Porcheddu A, De Luca L. Metal-free direct oxidation of aldehydes to esters using TCCA. Org Lett 2015; 17: 3666-3669 DOI: 10.1021/acs.orglett.5b01579.
- 27 Hunsen M. Carboxylic Acids from Primary Alcohols and Aldehydes by a Pyridinium Chlorochromate Catalyzed Oxidation. In: Synthesis. Stuttgart: Thieme; 2005: 2487-2490
- 28 Sancineto L, Tidei C, Bagnoli L, Marini F, Lenardão EJ, Santi C. Selenium catalyzed oxidation of aldehydes: Green synthesis of carboxylic acids and esters. Molecules 2015; 20: 10496-10510
- 29 Brzaszcz M, Kloc K, Maposah M. Selenium (IV) oxide catalyzed oxidation of aldehydes to carboxylic acids with hydrogen peroxide. Synthetic Communications 2000; 30: 4425-4434
- 30 Nikou T, Liaki V, Stathopoulos P, Sklirou AD, Tsakiri EN, Jakschitz T, Bonn G, Trougakos IP, Halabalaki M, Skaltsounis LA. Comparison survey of EVOO polyphenols and exploration of healthy aging-promoting properties of oleocanthal and oleacein. Food Chem Toxicol 2019; 125: 403-412
- 31 International Olive Council. Trade standard applying to olive oils and olive pomance oils. COI/T15/NC 3/Rev2 2006.
- 32 EEC EU. Regulation No 2568/91 on the characteristics of olive oil and olive-residue and on the relevant methods of analysis. Off J Eur Communities 1991; 34: L248