Metabolomic fingerprinting and genetic discrimination of four Hypericum taxa from Greece Author Zeliou, Konstantina ∗ & Laboratory of Pharmacognosy and Chemistry of Natural Products, Department of Pharmacy, University of Patras, 26504 Patras, Greece Author Koui, Eirini-Maria Author Papaioannou, Charikleia Author Koulakiotis, Nikolaos Stavros Author Iatrou, Gregoris Author Tsarbopoulos, Anthony Author Papasotiropoulos, Vassilis Author Lamari, Fotini N. text Phytochemistry 2020 112290 2020-06-30 174 1 15 http://dx.doi.org/10.1016/j.phytochem.2020.112290 journal article 10.1016/j.phytochem.2020.112290 1873-3700 8295050

Table 1 Main volatile metabolites in essential oils of the four Hypericum taxa using GC/MS.

Compound	RIlit	RIcal	H. perforatum ssp. veronense	H. perfoliatum	H. triquetrifolium	H. empetrifolium ssp. empetrifolium
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2–Methyloctane	860 D	875	1.25 ± 0.07	n.d.	n.d.	n.d.
n –Nonane	902 A	901	0.33 ± 0.02	n.d.	0.35 ± 0.02	n.d.
α –Pinene	940 A	935	7.49 ± 0.12	0.23 ± 0.02	1.59 ± 0.09	18.69 ± 0.32
Camphene	948 A	950	0.40 ± 0.01	n.d.	tr	0.26 ± 0.02
3–Methyl–nonane	971 D	969	0.24 ± 0.02	n.d.	3.18 ± 0.21	n.d.
β –Pinene	977 A, D	979	1.01 ± 0.06	0.23 ± 0.01	0.48 ± 0.02	7.68 ± 0.32
α –Myrcene	994 D	992	0.62 ± 0.03	tr	0.34 ± 0.02	2.06 ± 0.17
α –Terpinene	1008 A	1018	tr	tr	tr	0.28 ± 0.01
ο –Cymene	1022 F	1025	0.17 ± 0.01	tr	tr	tr
D–Limonene	1027 A	1030	0.40 ± 0.03	0.17 ± 0.00	0.33 ± 0.01	3.72 ± 0.11
1,8–Cineole	1029 A	1032	2.00 ± 0.12	n.d.	tr	0.50 ± 0.03
(Z)– β –Ocimene	1035 A	1037	tr	0.35 ± 0.01	tr	tr
(E)– β –Ocimene	1040 A	1048	0.43 ± 0.02	n.d.	tr	0.23 ± 0.01
γ –Terpinene	1056 A	1059	tr	tr	tr	0.75 ± 0.05
2–Methyl–decane	1067 D	1063	0.69 ± 0.04	tr	1.99 ± 0.09	tr
Terpinolene	1087 A	1090	tr	tr	tr	1.59 ± 0.13
n –Undecane	1100 D	1100	0.52 ± 0.03	4.21 ± 0.09	1.78 ± 0.08	0.29 ± 0.00
n –Nonanal	1104 A	1106	n.d.	0.39 ± 0.02	tr	n.d.
endo –Fenchol	1105 D	1115	n.d.	n.d.	tr	0.41 ± 0.02
allo –Ocimene	1133 D	1130	n.d.	0.18 ± 0.01	tr	tr
Camphor	1141 F	1146	1.55 ± 0.07	n.d.	tr	0.36 ± 0.01
Camphenehydrate	1150 D	1150	n.d.	n.d.	n.d.	0.23 ± 0.03
Isoborneol	1168 D	1164	n.d.	n.d.	n.d.	0.35 ± 0.03
Borneol	1163 A	1167	tr	tr	tr	0.79 ± 0.06
3–Methyl–undecane	1174 D	1170	n.d.	tr	tr	0.41 ± 0.02
Terpinen–4–ol	1179 D	1178	tr	tr	n.d.	0.22 ± 0.00
α –Terpineol	1192 D	1192	0.23 ± 0.00	0.36 ± 0.02	tr	2.21 ± 0.09
1–Dodecene a	1186–1199 #	1192	tr	n.d.	0.23 ± 0.02	n.d.
n –Decanal	1210 D	1207	n.d.	0.18 ± 0.02	n.d.	n.d.
2–Methyl–dodecane	1266 D	1260	0.63 ± 0.05	n.d.	tr	tr
δ –Elemene	1336 D	1333	0.43 ± 0.02	0.26 ± 0.00	tr	tr
α –Cubebene	1348 D	1345	tr	0.98 ± 0.10	0.36 ± 0.02	n.d.
α –Ylangene	1370 A	1366	tr	0.65 ± 0.04	tr	n.d.
α –Copaene	1375 A	1371	0.23 ± 0.01	2.22 ± 0.16	0.82 ± 0.04	tr
2– epi–α –Funebrene a	1380 $	1374	n.d.	0.34 ± 0.03	n.d.	n.d.
β –Bourbonene	1382 D	1382	0.25 ± 0.02	1.98 ± 0.05	tr	n.d.
β –Cubebene	1388 D	1383	n.d.	0.29 ± 0.03	tr	n.d.
β –Elemene b	1390 D	1390	3.43 ± 0.30	n.d.	n.d.	0.91 ± 0.12
1–Tetradecene a, b	1389 $	1391	tr	0.50 ± 0.04	0.54 ± 0.06	tr
α –Cedrene	1410 A	1411	0.24 ± 0.02	n.d.	tr	tr
E–β –Caryophyllene	1418 A	1414	10.27 ± 0.28	6.57 ± 0.32	27.90 ± 0.98	10.08 ± 0.88
β –Copaene	1426 D	1423	0.68 ± 0.05	2.51 ± 0.14	0.64 ± 0.01	0.87 ± 0.04
Aromadendrene	1437 A	1431	tr	0.75 ± 0.01	tr	n.d.
β –Gurjunene (Calarene)	1425 D	1436	0.28 ± 0.01	0.37 ± 0.00	0.38 ± 0.04	0.29 ± 0.04
α –Himachalene	1440 D	1440	n.d.	n.d.	0.26 ± 0.01	n.d.
α –Humulene	1452 A	1445	0.86 ± 0.06	2.14 ± 0.11	2.06 ± 0.07	1.50 ± 0.03
(Ε), β –Farnesene	1457 D	1452	2.10 ± 0.01	3.78 ± 0.21	0.47 ± 0.05	29.55 ± 1.09
cis –Cadina–1(6),4–diene	1455 D	1454	tr	0.41 ± 0.01	tr	n.d.
cis –Muurola–3,5–diene	1453 D	1457	n.d.	n.d.	tr	0.32 ± 0.03
2–Methyltetradecane	1460 E	1458	0.19 ± 0.00	0.41 ± 0.02	tr	n.d.
4,5–di– epi –Aristolochene	1476 F	1461	0.63 ± 0.05	n.d.	n.d.	n.d.
γ –Muurolene	1477 A	1469	1.19 ± 0.05	8.52 ± 0.34	3.40 ± 0.08	0.42 ± 0.06
D–Germacrene	1481 A	1473	5.52 ± 0.22	5.86 ± 0.47	2.99 ± 0.13	0.67 ± 0.01
4,11–Selinadiene a	1473–1485 #	1475	1.19 ± 0.27	n.d.	4.83 ± 0.39	n.d.
trans –Cadina 1(6),4–diene	1472 D	1476	n.d.	n.d.	n.d.	0.38 ± 0.04
β –Selinene	1483 D	1478	14.71 ± 0.57	0.22 ± 0.00	0.67 ± 0.09	n.d.
Amorpha–4,7(11)–diene	1485 D	1478	n.d.	n.d.	n.d.	0.20 ± 0.02
Eremophilene	1486 C	1480	1.50 ± 0.07	n.d.	n.d.	0.88 ± 0.04
cis –Muurola–4(14),5–diene	1467 E	1484	n.d.	0.27 ± 0.04	n.d.	n.d.
Valencene	1496 $	1486	n.d.	n.d.	4.66 ± 0.36	n.d.
α –Selinene	1491 D	1488	14.61 ± 0.65	n.d.	n.d.	0.72 ± 0.03
γ– Amorphene	1494 D	1489	n.d.	2.99 ± 0.31	1.24 ± 0.02	n.d.
trans –Muurola–4(14),5–diene	1488 D	1490	n.d.	n.d.	n.d.	0.98 ± 0.10
4– epi–cis –Dihydroagarofuran a	1499 $	1491	n.d.	n.d.	0.40 ± 0.03	n.d.
Epizonarene	1497 D	1494	n.d.	0.53 ± 0.02	tr	0.61 ± 0.02
(Ε,E)– α– Farnesene	1505 D	1494	0.50 ± 0.2	n.d.	n.d.	n.d.
α –Muurolene	1499 A	1495	n.d.	1.41 ± 0.11	0.66 ± 0.03	tr
(Z)– α –Bisabolene	1506 $	1501	n.d.	n.d.	0.67 ± 0.07	n.d.
δ –Amorphene	1506 D	1502	tr	0.18 ± 0.00	0.25 ± 0.02	0.50 ± 0.02
γ –Cadinene	1513 A	1507	0.71 ± 0.06	5.26 ± 0.48	2.04 ± 0.31	0.41 ± 0.02
7– epi–a –Selinene	1520 F	1509	0.50 ± 0.00	tr	0.63 ± 0.05	tr
trans –Calamene	1520 C	1515	n.d.	0.72 ± 0.08	tr	tr
δ –Cadinene	1523 D	1516	1.26 ± 0.08	7.80 ± 0.28	3.08 ± 0.06	1.36 ± 0.14
trans –Cadina–1,4–diene	1532 A	1523	tr	1.02 ± 0.07	0.32 ± 0.02	n.d.