QUANTITATIVE MEASUREMENT OF FOUR MAJOR SECOIRIDOID DERIVATIVES IN OLIVE. OIL USING qnmr. PROOF OF THE ARTIFICIAL FORMATION OF ALDEHYDIC OLEUROPEIN AND

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1 QUANTITATIVE MEASUREMENT OF FOUR MAJOR SECOIRIDOID DERIVATIVES IN OLIVE OIL USING qnmr. PROOF OF THE ARTIFICIAL FORMATION OF ALDEHYDIC OLEUROPEIN AND LIGSTROSIDE AGLYCON ISOMERS EVANGELIA KARKOULA, ANGELIKI SKANTZARI, ELENI MELLIOU,, PROKOPIOS MAGIATIS,* Laboratory of Pharmacognosy and Natural Products Chemistry, Faculty of Pharmacy, University of Athens, Panepistimiopolis Zografou, Athens, Greece, Olive Center, University of California, Davis CA *Corresponding author (Tel: ; Fax: ; University of Athens University of California, Davis

2 Supplementary table 1. Oleocanthal (p-hpea-eda), oleacein (3,4-DHPEA EDA), aldehydic form of oleuropein aglycon (3,4-DHPEA-EA) and aldehydic form of ligstroside aglycon (p-hpea-ea) levels in olive oil samples from Greece. D1=Oleocanthal+oleacein, D2=oleacein/oleocanthal. D3=the sum of the four compounds. The values are means of two measurements. VARIETY ORIGIN YEAR Harvest season Analysis date Oleocanthal mg/kg Oleacein mg/kg D2 D1 Oleuropein aglycon mg/ kg Ligstroside aglycon. mg/ kg ADRAMYTINI LESVOS - ALL PERIOD MARCH ND ND ND ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD MARCH ND ND ND ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD MARCH ND ND ND ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD JULY ND ND ND ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD JULY ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD JULY ND ND ND ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD JULY ND ND ND ND ND ND ND ADRAMYTINI LESVOS - ALL PERIOD JULY AGOUROMANAKI KORINTHIA - ALL PERIOD MARCH ND ND AGOUROMANAKI KORINTHIA - DECEMBER MARCH ND ATHENOLIA LAKONIA ALL PERIOD JANUARY ATHENOLIA LAKONIA ALL PERIOD JANUARY ND ATHENOLIA LAKONIA - ALL PERIOD JULY ATHENOLIA LAKONIA - ALL PERIOD JULY ND ND ATHENOLIA LAKONIA - ALL PERIOD JANUARY ATHENOLIA LAKONIA - NOVEMBER DECEMBER D3

3 ATHENOLIA CRETE - ALL PERIOD MARCH ATHENOLIA LAKONIA - ALL PERIOD MARCH ATHENOLIA LAKONIA - ALL PERIOD MARCH ATHENOLIA LAKONIA - DECEMBER MAY ATHENOLIA LAKONIA - OCTOBER DECEMBER ATHENOLIA LAKONIA - NOVEMBER DECEMBER ND ATHENOLIA LAKONIA - NOVEMBER DECEMBER ATHENOLIA LAKONIA - NOVEMBER JANUARY ATHENOLIA LAKONIA - NOVEMBER JANUARY ATHENOLIA LAKONIA - NOVEMBER JANUARY ATHENOLIA LAKONIA - NOVEMBER JANUARY ATHENOLIA EVIA - ALL PERIOD MARCH ATHENOLIA EVIA - ALL PERIOD MARCH ATHENOLIA. MESSINIA - OCTOBER OCTOBER CHALKIDIKI KAVALA - OCTOBER NOVEMBER CHALKIDIKI KAVALA - OCTOBER NOVEMBER CHALKIDIKI KAVALA - SEPTEMBER DECEMBER CHALKIDIKI KAVALA - OCTOBER DECEMBER CHALKIDIKI KAVALA - OCTOBER DECEMBER CHALKIDIKI KAVALA - OCTOBER JANUARY ND CHALKIDIKI CHALKIDIKI - OCTOBER FEBRUARY

4 CHALKIDIKI KAVALA - OCTOBER FEBRUARY CHALKIDIKI CHALKIDIKI - ALL PERIOD JANUARY ND ND CHALKIDIKI CHALKIDIKI - ALL PERIOD JANUARY ND ND CHALKIDIKI KAVALA - OCTOBER OCTOBER CHALKIDIKI KOZANI - NOVEMBER DECEMBER CHALKIDIKI KAVALA - OCTOBER JANUARY CHALKIDIKI KAVALA - OCTOBER JANUARY CHALKIDIKI KAVALA - OCTOBER JANUARY CHALKIDIKI KOZANI - ALL PERIOD JANUARY CHALKIDIKI KAVALA - ALL PERIOD FEBRUARY CHALKIDIKI KAVALA - ALL PERIOD FEBRUARY ND ND CHALKIDIKI KAVALA - ALL PERIOD FEBRUARY CHALKIDIKI KAVALA - ALL PERIOD MARCH CONSERVOLEA MAGNESIA - NOVEMBER NOVEMBER CONSERVOLEA MAGNESIA - NOVEMBER NOVEMBER ND CONSERVOLEA MAGNESIA - NOVEMBER JANUARY CONSERVOLEA MAGNESIA - ALL PERIOD JANUARY ND ND CONSERVOLEA PHTHIOTIDA - ALL PERIOD MARCH ND

5 CONSERVOLEA THESPROTIA - NOVEMBER MARCH KOLOVI LESVOS - ALL PERIOD MARCH KOLOVI LESVOS - ALL PERIOD JULY ND ND ND KOLOVI LESVOS - ALL PERIOD JULY ND KOLOVI LESVOS - ALL PERIOD JULY KOLOVI LESVOS - ALL PERIOD JANUARY KOLOVI LESVOS - DECEMBER MARCH KORONEIKI MESSINIA ALL PERIOD NOVEMBER ND KORONEIKI CRETE JANUARY DECEMBER KORONEIKI ATTIKI - ALL PERIOD NOVEMBER KORONEIKI ZAKYNTHOS - ALL PERIOD MARCH ND KORONEIKI CRETE - JANUARY MARCH KORONEIKI LAKONIA - FEBRUARY MARCH KORONEIKI LAKONIA - FEBRUARY MARCH KORONEIKI ZAKYNTHOS - NOVEMBER DECEMBER KORONEIKI LAKONIA - ALL PERIOD JULY KORONEIKI ILIA - ALL PERIOD JULY ND KORONEIKI ILIA - ALL PERIOD JULY ND ND KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY

6 KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI CRETE - ALL PERIOD JULY ND KORONEIKI CRETE - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - JANUARY MAY ND KORONEIKI ILIA - DECEMBER DECEMBER KORONEIKI LEFKADA - ALL PERIOD JANUARY KORONEIKI LAKONIA - DECEMBER JANUARY KORONEIKI LAKONIA - DECEMBER DECEMBER KORONEIKI MESSINIA - NOVEMBER- DECEMBER JANUARY KORONEIKI CRETE - DECEMBER DECEMBER KORONEIKI ILIA - NOVEMBER DECEMBER KORONEIKI ZAKYNTHOS - NOVEMBER DECEMBER KORONEIKI ZAKYNTHOS - NOVEMBER DECEMBER KORONEIKI ILIA - DECEMBER DECEMBER KORONEIKI ILIA - ALL PERIOD JANUARY KORONEIKI CRETE - DECEMBER JANUARY KORONEIKI LAKONIA - DECEMBER DECEMBER

7 KORONEIKI KEFALONIA - NOVEMBER NOVEMBER KORONEIKI KORINTHIA - NOVEMBER DECEMBER KORONEIKI EVIA - DECEMBER DECEMBER KORONEIKI EVIA - DECEMBER DECEMBER KORONEIKI MESSINIA - NOVEMBER DECEMBER KORONEIKI LAKONIA - NOVEMBER JANUARY KORONEIKI LAKONIA - NOVEMBER JANUARY KORONEIKI LAKONIA - NOVEMBER JANUARY KORONEIKI MESSINIA - JANUARY JANUARY ND KORONEIKI ILIA - DECEMBER JANUARY KORONEIKI ILIA - DECEMBER JANUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER- FEBRUARY DECEMBER KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY

8 KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER- DECEMBER FEBRUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER- FEBRUARY DECEMBER KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER- FEBRUARY DECEMBER KORONEIKI MESSINIA - NOVEMBER- DECEMBER FEBRUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY

9 KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - NOVEMBER- FEBRUARY DECEMBER KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI MESSINIA - NOVEMBER MARCH KORONEIKI MESSINIA - ALL PERIOD MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI MESSINIA - ALL PERIOD MARCH KORONEIKI CRETE - ALL PERIOD MARCH KORONEIKI ILIA - ALL PERIOD MARCH KORONEIKI PAROS - OCTOBER MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI MESSINIA - ALL PERIOD MARCH KORONEIKI MESSINIA - ALL PERIOD MAY ND ND KORONEIKI LAKONIA - ALL PERIOD MAY KORONEIKI MESSINIA - DECEMBER MAY KORONEIKI MESSINIA - NOVEMBER MAY KORONEIKI MESSINIA - DECEMBER MAY ND ND KORONEIKI MESSINIA - DECEMBER MAY KORONEIKI MESSINIA - DECEMBER MAY KORONEIKI MESSINIA - DECEMBER MAY KORONEIKI MESSINIA - ALL PERIOD MAY

10 KORONEIKI ATTIKI - NOVEMBER MAY KORONEIKI ATTIKI - ALL PERIOD JULY KORONEIKI ATTIKI - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY ND KORONEIKI MESSINIA - OCTOBER OCTOBER KORONEIKI PAROS - OCTOBER OCTOBER KORONEIKI PAROS - OCTOBER OCTOBER KORONEIKI ANTIPAROS - OCTOBER OCTOBER KORONEIKI ANTIPAROS - NOVEMBER DECEMBER KORONEIKI MESSINIA - NOVEMBER DECEMBER KORONEIKI ATTIKI - DECEMBER DECEMBER KORONEIKI LAKONIA - NOVEMBER DECEMBER KORONEIKI ZAKYNTHOS - NOVEMBER JANUARY KORONEIKI LAKONIA - DECEMBER JANUARY ND KORONEIKI LAKONIA - NOVEMBER JANUARY KORONEIKI ILIA - NOVEMBER JANUARY KORONEIKI ILIA - NOVEMBER JANUARY KORONEIKI MESSINIA - NOVEMBER JANUARY KORONEIKI CRETE - NOVEMBER JANUARY KORONEIKI LAKONIA - NOVEMBER JANUARY KORONEIKI ARGOLIDA - NOVEMBER JANUARY KORONEIKI ΑΧΑΙΑ - DECEMBER JANUARY KORONEIKI CRETE - NOVEMBER JANUARY KORONEIKI MESSINIA - DECEMBER JANUARY

11 KORONEIKI AITOLOAKARN ANIA - ALL PERIOD JANUARY ND ND KORONEIKI ZAKYNTHOS - NOVEMBER JANUARY KORONEIKI ZAKYNTHOS - NOVEMBER JANUARY KORONEIKI ZAKYNTHOS - NOVEMBER JANUARY KORONEIKI NAXOS - JANUARY FEBRUARY KORONEIKI MESSINIA - NOVEMBER FEBRUARY KORONEIKI LAKONIA - DECEMBER FEBRUARY KORONEIKI ILIA - ALL PERIOD FEBRUARY KORONEIKI LAKONIA - JANUARY FEBRUARY KORONEIKI LAKONIA - JANUARY FEBRUARY KORONEIKI CYPRUS - DECEMBER FEBRUARY KORONEIKI CYPRUS - JANUARY FEBRUARY KORONEIKI CYPRUS - JANUARY FEBRUARY KORONEIKI CRETE - ALL PERIOD FEBRUARY KORONEIKI CRETE - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI MESSINIA - ALL PERIOD FEBRUARY

12 KORONEIKI MESSINIA - ALL PERIOD FEBRUARY KORONEIKI CYPRUS - ALL PERIOD FEBRUARY KORONEIKI ILIA - ALL PERIOD MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI CRETE - ALL PERIOD MARCH KORONEIKI CRETE - ALL PERIOD MARCH KORONEIKI LAKONIA - ALL PERIOD MARCH KORONEIKI CRETE ALL PERIOD NOVEMBER KORONEIKI CRETE ALL PERIOD NOVEMBER KORONEIKI ZAKYNTHOS - NOVEMBER DECEMBER KORONEIKI ILIA - NOVEMBER DECEMBER KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY

13 KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KORONEIKI MESSINIA - ALL PERIOD JULY KOUTSOURELIA ACHAIA - DECEMBER JANUARY KOUTSOURELIA ACHAIA - DECEMBER APRIL ND ND LIANOLIA PREVEZA - NOVEMBER DECEMBER KERKYRAS LIANOLIA KERKYRAS PREVEZA - DECEMBER DECEMBER ND LIANOLIA PREVEZA - NOVEMBER- JANUARY

14 KERKYRAS DECEMBER LOCAL ZAKYNTHOS - NOVEMBER JANUARY MANAKI LAKONIA ALL PERIOD JANUARY ND MANAKI LAKONIA ALL PERIOD JANUARY MANAKI LAKONIA ALL PERIOD JANUARY MANAKI ARGOLIDA - ALL PERIOD JANUARY ND ND MANAKI ARGOLIDA - NOVEMBER DECEMBER ND MANAKI EVIA - DECEMBER DECEMBER ND MANAKI KORINTHIA - NOVEMBER JANUARY ND ND MANAKI ARGOLIDA - OCTOBER DECEMBER ND MANAKI PHTHIOTIDA - NOVEMBER DECEMBER ND MANAKI KORINTHIA - DECEMBER JANUARY MANAKI ARGOLIDA - NOVEMBER JANUARY ND MANAKI ARGOLIDA - OCTOBER JANUARY MANAKI ARGOLIDA - NOVEMBER JANUARY ND ND MANAKI ARGOLIDA - NOVEMBER JANUARY ND ND ND MANAKI ARGOLIDA - NOVEMBER JANUARY ND ND ND ND MANAKI ARGOLIDA - NOVEMBER DECEMBER ND ND

15 MEGARITIKI VIOTIA - NOVEMBER DECEMBER MEGARITIKI VIOTIA - NOVEMBER DECEMBER MEGARITIKI VIOTIA - NOVEMBER DECEMBER ND MEGARITIKI ATTIKI - NOVEMBER DECEMBER MEGARITIKI ATTIKI - DECEMBER DECEMBER ND ND MEGARITIKI ATTIKI - DECEMBER DECEMBER MEGARITIKI ATTIKI - DECEMBER DECEMBER ND ND MEGARITIKI VIOTIA - NOVEMBER JANUARY MEGARITIKI KOZANI - ALL PERIOD JANUARY MEGARITIKI ATTIKI - DECEMBER DECEMBER MEGARITIKI ATTIKI - NOVEMBER NOVEMBER ND MEGARITIKI ATTIKI - DECEMBER DECEMBER ND THIAKI ITHAKI - ALL PERIOD FEBRUARY THROUBA CHIOS - MARCH MARCH ND ND ND THROUBA CHIOS - MARCH MARCH THROUBA THASSOS - NOVEMBER JULY THROUBA THASSOS - NOVEMBER JULY THROUBA THASSOS - NOVEMBER JULY THROUBA THASSOS - OCTOBER JULY THROUBA THASSOS - NOVEMBER DECEMBER

16 THROUBA THASSOS - NOVEMBER DECEMBER THROUBA THASSOS - NOVEMBER DECEMBER THROUBA THASSOS - NOVEMBER DECEMBER THROUBA THASSOS - NOVEMBER JANUARY THROUBA THASSOS - NOVEMBER JANUARY THROUBA THASSOS - NOVEMBER JANUARY THROUBA THASSOS - NOVEMBER JANUARY THROUBA THASSOS - ALL PERIOD MARCH ND ND THROUBA THASSOS - ALL PERIOD MARCH THROUBA THASSOS - ALL PERIOD MARCH THROUBA THASSOS - ALL PERIOD MARCH THROUBA THASSOS - ALL PERIOD MARCH THROUBA THASSOS - ALL PERIOD MARCH THROUBA THASSOS NOVEMBER 2009 DECEMBER THROUBA THASSOS - NOVEMBER MAY THROUBA THASSOS - NOVEMBER MAY THROUBA THASSOS - NOVEMBER MAY THROUBA THASSOS - ALL PERIOD MAY THROUBA THASSOS - ALL PERIOD MAY THROUBA KAVALA - NOVEMBER JANUARY THROUBA KAVALA - NOVEMBER JANUARY THROUBA KAVALA - NOVEMBER JANUARY THROUBA KAVALA - NOVEMBER JANUARY ND ND THROUBA KAVALA - NOVEMBER JANUARY ND ND

17 THROUBA KAVALA - NOVEMBER JANUARY THROUBA KAVALA - NOVEMBER DECEMBER WILD MESSINIA - JANUARY JANUARY ND ND WILD MAGNESIA - ALL PERIOD JULY ND WILD PHTHIOTIDA - OCTOBER OCTOBER ND WILD PHTHIOTIDA - OCTOBER OCTOBER ND WILD CRETE - OCTOBER OCTOBER WILD MAGNESIA - NOVEMBER NOVEMBER WILD LAKONIA - NOVEMBER NOVEMBER WILD CRETE - DECEMBER DECEMBER ND ND WILD MAGNESIA - NOVEMBER DECEMBER ND: not detected

18 1 2 Supplementary table 2. Oleocanthal and oleacein levels in olive oil samples from California VARIETY YEAR Analysis date oleocanthal mg/kg oleacein mg/kg D2 D1 Oleuropei n aglycon mg/ Kg Ligstroside aglycon. mg/ Kg D3 MISSION a - MAY MISSION - MAY MISSION - MAY MISSION - MAY MISSION - MAY BAROUNI - MAY MANZANILLO - MAY MISSION - MAY MISSION - MAY MISSION - MAY MISSION - MAY LECCINO - SEPTEMBER FRANTOIO - SEPTEMBER ARBEQUINA - SEPTEMBER ND

19 MISSION - SEPTEMBER MISSION - SEPTEMBER TAGIASCA - SEPTEMBER PICUAL - FEBRUARY MISSION - FEBRUARY MISSION WILD - FEBRUARY a : In Mission variety oleacein was partially overlapped and the presented oleacein values may be overestimated. ND: not detected

20 Detailed description of the isolation of 5S,8R,9S methyl elenolate. Olive oil cv Koroneiki (500 g) was mixed with cyclohexane (2 L) and extracted with acetonitrile (2.5 L). The acetonitrile phase was collected and washed with cyclohexane (2 L). The acetonitrile phase was collected and evaporated using a rotary evaporator under reduced pressure. The residue (880 mg) was submitted to column chromatography using Si gel 60 Merck (40-63 µm) as stationery phase and mobile phase as shown in the following supplementary table: Mobile phase cycloexane : EtOAc FRACTIONS VOLUME (ml) 100 % chex chex: 5 EtOAc chex: 10 EtOAc chex: 12 EtOAc chex: 15 EtOAc chex: 20 EtOAc chex: 25 EtOAc chex: 50 EtOAc % EtOAc Fractions contained ligstroside aglycon (73 mg), fractions (46 mg) contained oleocanthal, fractions contained oleuropein aglycon (109 mg) and fractions (59 mg) contained oleacein. All fractions were purified by preparative TLC using cyclohexane/ethyl acetate: 30/70 as mobile phase. The corresponding zones were extracted from the stationary phase using ethyl acetate under sonication for 15 min. The solvent was filtered and evaporated. The above procedure was performed twice until maximum purity was achieved for each compound. Fraction (5 mg) contained methyl elenolate

21 20 NMR data of 5S,8R,9S methyl elenolate Atom 13 C-NMR (δ ppm) 1 Η-NMR (δ ppm, J Hz) (1H, quint, J=6.5 Hz) (1H, td, J = 5.9, 1.8 Hz) (1H, m) (1H, s) (3H, d, J = 6.8 Hz) (1H, d, J = 1.8 Hz) 6a 6b (1H, dd, J= 16.2 Hz, J= 3.9 Hz) 2.54 (1H, q, J= 16.2 Hz, J= 9.4 Hz) COOMe (7) (3H, s) COOMe (11) (3H, s)

22 Fig. S1 Characteristic chemotypes identified regarding the main secoiridoids found in olive oil. A: Domination of decarboxymethyl dialdehydic forms (oleocanthal(1), oleacein (2))(e.g. cv Koroneiki, cv Throuba, cv. Athenolia, cv.leccino, cv. Arbequina, cv.frantoio), B: domination of monoaldehyde aglycons (3,4)(e.g.. cv.mission, cv Picual), C: absence (or significantly reduced content) of both categories (e.g. cv. Adramytini, cv.megaritiki, cv. Manaki). D: Example of a sample presenting yet uncharacterized aldehyde protons with intensity higher than that of oleocanthal and oleacein.

23 Fig. S2. 1H-NMR of methyl elenolate.

24 Fig. S3: 13 C-NMR spectrum of methyl elenolate

25 Fig. S4: HMQC spectrum of methyl elenolate

26 Fig. S5: HMBC spectrum of methyl elenolate

27 Fig. S6: COSY spectrum of methyl elenolate

28 Fig. S7: NOESY spectrum of methyl elenolate.

29 Oleacein (int.) Oleocanthal (integration) Fig. S8 D2 distribution (Oleacein/Oleocanthal ratio) for koroneiki variety from a specific geographic origin (Messinia) Fig. S9 Relation between olecanthal and D3 index in all studied olive oils from Greece

PRESS RELEASE. Graph 1: Road traffic accidents and casualties, January January Jul-14. Jul-15. Apr-15. Jan-15. Oct-15.

PRESS RELEASE. Graph 1: Road traffic accidents and casualties, January January Jul-14. Jul-15. Apr-15. Jan-15. Oct-15. Jan-11 Apr-11 Jul-11 Oct-11 Jan-12 Apr-12 Jul-12 Oct-12 Jan-13 Apr-13 Jul-13 Oct-13 Jan-14 Apr-14 Jul-14 Oct-14 Jan-15 Apr-15 Jul-15 Oct-15 Jan-16 Apr-16 Jul-16 Oct-16 Jan-17 Apr-17 Jul-17 Oct-17 Jan-18