2.1. Phytochemical Investigation
The complete compositions and the extraction yields of the essential oils (EOs) obtained from the dried aerial part of the samples are reported in Table 1. The following taxa acronyms were used: Boule = S. rosmarinus ‘Boule’, Gori = S. rosmarinus ‘Gorizia’, Joyce = S. rosmarinus ‘Joyce de Baggio’, Vicom = S. rosmarinus ‘Vicomte de Noailles’, and Jord = S. jordanii. Overall, 65 compounds were identified, accounting for 98.6–100% of the total composition.
Table 1. Complete composition and extraction yield (% w/w dry weight) of the essential oil obtained from the samples of S. rosmarinus and S. jordanii.
Peak |
Compounds |
l.r.i. |
Class. |
Relative Abundances (%) ±SD |
Boule |
Gori |
Joyce |
Vicom |
Jord |
1 |
tricyclene |
922 |
mh |
- |
0.1 ± 0.00 |
- |
- |
0.1 ± 0.01 |
2 |
α-thujene |
926 |
mh |
- |
0.2 ± 0.02 |
0.1 ± 0.00 |
0.2 ± 0.02 |
- |
3 |
α-pinene |
933 |
mh |
37.3 ± 3.09 |
6.4 ± 0.10 |
25.6 ± 0.02 |
4.1 ± 0.04 |
3.1 ± 0.17 |
4 |
camphene |
948 |
mh |
2.9 ± 0.09 |
4.3 ± 0.04 |
2.0 ± 0.09 |
3.3 ± 0.10 |
3.9 ± 0.06 |
5 |
thuja-2,4(10)-diene |
954 |
mh |
0.3 ± 0.02 |
- |
0.4 ± 0.07 |
- |
- |
6 |
β-pinene |
977 |
mh |
0.5 ± 0.04 |
4.2 ± 0.40 |
1.8 ± 0.07 |
1.6 ± 0.03 |
0.9 ± 0.01 |
7 |
3-octanone |
985 |
nt |
- |
1.0 ± 0.17 |
- |
- |
- |
8 |
myrcene |
991 |
mh |
2.0 ± 0.16 |
0.6 ± 0.01 |
0.9 ± 0.09 |
0.4 ± 0.03 |
0.2 ± 0.02 |
9 |
α-phellandrene |
1006 |
mh |
- |
1.2 ± 0.05 |
0.2 ± 0.00 |
- |
- |
10 |
δ-3-carene |
1011 |
mh |
- |
0.4 ± 0.01 |
- |
- |
- |
11 |
α-terpinene |
1017 |
mh |
0.2 ± 0.01 |
0.5 ± 0.02 |
0.5 ± 0.01 |
0.3 ± 0.01 |
0.7 ± 0.01 |
12 |
p-cymene |
1025 |
mh |
2.8 ± 0.22 |
1.0 ± 0.23 |
0.8 ± 0.08 |
1.8 ± 0.09 |
1.6 ± 0.06 |
13 |
limonene |
1029 |
mh |
3.3 ± 0.11 |
3.6 ± 0.05 |
2.1 ± 0.12 |
1.7 ± 0.14 |
1.7 ± 0.03 |
14 |
1,8-cineole |
1031 |
om |
11.4 ± 0.22 |
20.5 ± 0.73 |
23.9 ± 0.42 |
20.0 ± 0.64 |
11.5 ± 0.11 |
15 |
(Z)-β-ocimene |
1036 |
om |
- |
- |
- |
- |
1.2 ± 0.10 |
16 |
γ-terpinene |
1058 |
mh |
0.4 ± 0.03 |
1.0 ± 0.10 |
0.9 ± 0.02 |
0.6 ± 0.02 |
0.7 ± 0.02 |
17 |
cis-sabinene hydrate |
1066 |
om |
- |
0.3 ± 0.02 |
- |
0.1 ± 0.01 |
0.1 ± 0.01 |
18 |
terpinolene |
1089 |
mh |
0.5 ± 0.02 |
0.6 ± 0.01 |
0.7 ± 0.03 |
0.4 ± 0.00 |
0.2 ± 0.01 |
19 |
trans-sabinene hydrate |
1098 |
om |
- |
0.1 ± 0.02 |
- |
- |
- |
20 |
linalool |
1101 |
om |
1.5 ± 0.01 |
0.4 ± 0.04 |
2.1 ± 0.14 |
0.2 ± 0.01 |
- |
21 |
filifolone |
1108 |
om |
0.2 ± 0.00 |
- |
- |
- |
- |
22 |
fenchol |
1114 |
om |
0.1 ± 0.01 |
- |
- |
- |
- |
23 |
cis-p-menth-2-en-1-ol |
1122 |
om |
- |
- |
0.2 ± 0.03 |
- |
- |
24 |
α-campholenal |
1125 |
om |
- |
- |
- |
0.2 ± 0.01 |
- |
25 |
chrysanthenone |
1126 |
om |
0.8 ± 0.05 |
0.2 ± 0.06 |
0.2 ± 0.01 |
- |
- |
26 |
trans-pinocarveol |
1139 |
om |
0.2 ± 0.02 |
0.1 ± 0.02 |
- |
- |
- |
27 |
cis-verbenol |
1142 |
om |
- |
0.1 ± 0.03 |
0.1 ± 0.03 |
- |
- |
28 |
camphor |
1145 |
om |
7.7 ± 0.22 |
16.9 ± 1.35 |
3.3 ± 0.50 |
42.2 ± 0.52 |
33.4 ± 0.38 |
29 |
trans-pinocampone |
1160 |
om |
0.3 ± 0.01 |
- |
0.2 ± 0.01 |
0.2 ± 0.02 |
- |
30 |
pinocarvone |
1163 |
om |
0.2 ± 0.00 |
0.3 ± 0.02 |
0.3 ± 0.03 |
0.3 ± 0.07 |
- |
31 |
borneol |
1165 |
om |
2.5 ± 0.11 |
6.5 ± 0.00 |
3.7 ± 0.26 |
0.6 ± 0.13 |
14.6 ± 0.01 |
32 |
isopinocampheol |
1173 |
om |
0.4 ± 0.04 |
- |
- |
- |
- |
33 |
cis-pinocamphone |
1174 |
om |
- |
0.8 ± 0.02 |
0.8 ± 0.01 |
0.5 ± 0.00 |
- |
34 |
4-terpineol |
1177 |
om |
1.4 ± 0.08 |
0.9 ± 0.08 |
1.1 ± 0.01 |
1.2 ± 0.02 |
2.8 ± 0.03 |
35 |
p-cymen-8-ol |
1185 |
om |
0.1 ± 0.01 |
- |
- |
0.2 ± 0.01 |
- |
36 |
α-terpineol |
1191 |
om |
2.6 ± 0.19 |
2.0 ± 0.24 |
2.4 ± 0.09 |
2.8 ± 0.07 |
2.9 ± 0.06 |
37 |
myrtenol |
1195 |
om |
0.2 ± 0.02 |
0.2 ± 0.02 |
0.4 ± 0.14 |
0.2 ± 0.03 |
- |
38 |
verbenone |
1210 |
om |
12.8 ± 2.67 |
1.9 ± 0.15 |
14.9 ± 0.27 |
2.7 ± 0.03 |
0.6 ± 0.02 |
39 |
trans-carveol |
1219 |
om |
0.1 ± 0.06 |
- |
- |
0.2 ± 0.04 |
- |
40 |
carvone |
1244 |
om |
- |
- |
- |
0.1 ± 0.03 |
- |
41 |
geraniol |
1254 |
om |
0.5 ± 0.08 |
- |
3.9 ± 0.15 |
- |
- |
42 |
trans-ascaridol glycol |
1268 |
om |
- |
0.4 ± 0.10 |
- |
- |
- |
43 |
geranial |
1271 |
om |
- |
- |
0.3 ± 0.02 |
- |
- |
44 |
bornyl acetate |
1286 |
om |
3.9 ± 0.45 |
6.5 ± 0.50 |
2.6 ± 0.17 |
0.2 ± 0.01 |
10.8 ± 0.06 |
45 |
myrtenyl acetate |
1326 |
om |
- |
- |
0.1 ± 0.00 |
- |
- |
46 |
eugenol |
1357 |
pp |
- |
- |
- |
- |
0.4 ± 0.02 |
47 |
α-copaene |
1376 |
sh |
- |
0.3 ± 0.05 |
- |
- |
- |
48 |
geranyl acetate |
1385 |
om |
- |
- |
0.5 ± 0.03 |
- |
- |
49 |
(Z)-jasmone |
1397 |
nt |
0.4 ± 0.07 |
- |
- |
- |
- |
50 |
methyl eugenol |
1407 |
pp |
- |
- |
0.3 ± 0.02 |
- |
- |
51 |
β-caryophyllene |
1419 |
sh |
0.2 ± 0.03 |
6.7 ± 1.51 |
1.1 ± 0.15 |
0.6 ± 0.06 |
3.1 ± 0.08 |
52 |
α-humulene |
1453 |
sh |
- |
1.9 ± 0.39 |
0.3 ± 0.04 |
- |
3.2 ± 0.10 |
53 |
γ-muurolene |
1477 |
sh |
- |
0.4 ± 0.08 |
- |
- |
- |
54 |
bicyclogermacrene |
1496 |
sh |
- |
0.3 ± 0.05 |
- |
- |
- |
55 |
trans-γ-cadinene |
1514 |
sh |
- |
0.4 ± 0.07 |
- |
- |
- |
56 |
δ-cadinene |
1524 |
sh |
- |
0.9 ± 0.20 |
- |
- |
- |
57 |
caryophyllene oxide |
1582 |
os |
0.4 ± 0.09 |
4.3 ± 0.16 |
0.6 ± 0.10 |
1.5 ± 0.24 |
0.8 ± 0.02 |
58 |
humulene oxide II |
1608 |
os |
0.3 ± 0.07 |
0.5 ± 0.08 |
- |
- |
0.6 ± 0.03 |
59 |
caryophylla-4(14),8(15)-dien-5-ol (unidentified isomer) |
1633 |
os |
- |
0.2 ± 0.06 |
- |
0.3 ± 0.04 |
- |
60 |
T-cadinol |
1641 |
os |
- |
0.3 ± 0.03 |
- |
0.2 ± 0.03 |
- |
61 |
α-bisabolol oxide B |
1655 |
os |
- |
- |
- |
0.8 ± 0.06 |
- |
62 |
14-hydroxy-9-epi-(E)-caryophyllene |
1670 |
os |
- |
- |
- |
7.1 ± 1.76 |
0.2 ± 0.01 |
63 |
α-bisabolol |
1685 |
os |
- |
- |
- |
- |
0.4 ± 0.01 |
64 |
trans-ferruginol |
2325 |
od |
0.2 ± 0.04 |
0.2 ± 0.01 |
- |
- |
- |
|
Total identified (%) |
|
|
98.6 ± 0.06 |
98.7 ± 0.31 |
99.1 ± 0.16 |
96.6 ± 0.16 |
100 ± 0.03 |
|
|
|
|
Boule |
Gori |
Joyce |
Vicom |
Jord |
|
Monoterpene hydrocarbons (mh) |
|
50.2 ± 3.77 A |
24.0 ± 0.54 C |
36.0 ± 0.19 B |
14.3 ± 0.46 D |
14.2 ± 0.49 D |
|
Oxygenated monoterpenes (om) |
|
46.9 ± 3.42 C |
57.5 ± 2.08 B |
60.9 ± 0.04 B |
71.9 ± 1.55 A |
77.1 ± 0.25 A |
|
Sesquiterpene hydrocarbons (sh) |
|
0.2 ± 0.03 C |
10.7 ± 2.35 A |
1.3 ± 0.19 C |
0.6 ± 0.06 C |
6.3 ± 0.18 B |
|
Oxygenated sesquiterpenes (os) |
|
0.7 ± 0.16 C |
5.3 ± 0.33 B |
0.6 ± 0.10 C |
9.8 ± 2.12 A |
2.0 ± 0.07 C |
|
Oxygenates diterpenes (od) |
|
0.2 ± 0.04 A |
0.2 ± 0.01 A |
- B |
- B |
- B |
|
Phenylpropanoids (pp) |
|
- |
- |
0.3 ± 0.02 |
- |
0.4 ± 0.02 |
|
Other non-terpene derivates (nt) |
|
0.4 ± 0.07 B |
1.0 ± 0.17 A |
- C |
- C |
- C |
|
EO Extraction yield (%w/w) |
|
0.57 ± 0.02 C |
1.17 ± 0.16 B |
0.76 ± 0.04 C |
2.25 ± 0.15 A |
0.71 ± 0.04 C |
According to Flamini et al. (2020) [
2] monoterpenes are the main class of compounds in
Rosmarinus genus: indeed, the EO obtained from
S. rosmarinus ‘Boule’ was characterized by a predominance of their hydrocarbon derivatives (50.2%), while those obtained from the other four samples presented more oxygenated ones.
Nevertheless, monoterpene hydrocarbons were well-represented in all the samples, accounting for up to 50.2% in Boule, followed by Joyce (36.0%), Gori (24.0%), Jord, and Vicom (14.3 and 14.2%, respectively). α-Pinene, camphene, β-pinene, and limonene were the main chemicals of this class, but only the first reached considerable relative amounts, up to 37.3% in ‘Boule’ and 25.6% in ‘Joyce’.
Oxygenated monoterpenes, indeed, resulted more abundant in Jord and Vicom (77.1% and 71.9%, respectively), followed by Joyce and Gori (60.9% and 57.5%, respectively) and Boule (46.9%). Within this chemical class, 1,8-cineole (11.4–23.9%), camphor (3.3–42.2%), borneol (0.6–14.6%), 4-terpineol 0.9–2.8%), α-terpineol (2.0–2.9%), verbenone (0.6–14.9%), and bornyl acetate (0.2–10.8%) were the most representative compounds, as they were detected in all the samples, even though with a high variability in their relative abundances.
Sesquiterpenes were also detected in appreciable relative amounts: the EOs obtained from Gori and Jord presented a predominance of the hydrocarbons form, and Vicom of the oxygenated form. In Boule and Joyce, this chemical class was poorly represented. β-Caryophyllene (0.2–6.7%) and caryophyllene oxide (0.4–4.3%) were identified in each sample; noteworthy was the amount of 14-hydroxy-9-epi-(E)-caryophyllene in Vicom (7.1%).
All the most representative compounds detected in the EOs were typical chemicals of the essential oils of
S. rosmarinus [
9] and
S. jordanii [
5,
14].
The EO extraction yield presented significant differences among the samples: Vicom was the most productive one (2.25% w/w), followed by Gori (1.17% w/w), while Joyce, Jord, and Boule presented the lowest yields (0.76 > 0.71 > 0.56% w/w, respectively).
This is the first time that the essential oil composition of the four cultivars of S. rosmarinus (‘Boule’; ‘Vicomte de Noailles’; ‘Gorizia’; ‘Joyce de Baggio’) was reported to better employ this plant material not only as ornamental display items but also as derivative products for industrial use.
Statistical Analysis
The first axis of PCA explained 62.4% of variance, the second axis (PCA2) a further 25.1% (Figure 1). Vicom segregated alone, while the other taxa were distributed into two groups, one formed by Gori and Jord, and the other one made up by Boule and Joyce. Nine chemical compounds showed a significant discriminative function between the taxa. Vicom was characterized by high amounts of camphor (28) and 14-hydroxy-9-epi-(E)-caryophyllene (62). Gori and Jord differed in their predominance of camphene (4), borneol (31), bornyl acetate (44), and α-humulene (52). Lastly, Boule and Joyce were characterized by high amounts of α-pinene (3), myrcene (8), and verbenone (38).
Figure 1. PCA of the matrix 5 taxa × 18 compounds. Compounds with a Pearson correlation coefficient > 0.8 with the first two PCA axes are shown. Abbreviations of chemical compounds: 3 = α-pinene, 4 = camphene, 8 = myrcene, 28 = camphor, 31 = borneol, 38 = verbenone, 44 = bornyl acetate, 52 = α-humulene, 62 = 14-hydroxy-9-epi-(E)-caryophyllene.