Thermo-Oxidative Decomposition of Lovage (Levisticum officinale) and Davana (Artemisia pallens) Essential Oils under Simulated Tobacco Heating Product Conditions

No.	t_ret/min	MW	Compound	Injection /area-% aver. ± std. dev.	Pyrolysis /area-% aver. ± std. dev.	Difference in area-%	Significance level ^a
1	10.45	136	α-Pinene	0.74 ± 0.10	0.22 ± 0.08	−0.52	***
2	11.03	136	Camphene	0.21 ± 0.03	0.10 ± 0.03	−0.11	***
3	11.74	114	Heptanal	0	0.49 ± 0.10	+0.49	***
4	11.86	136	β-Pinene	1.23 ± 0.15	0.66 ± 0.18	−0.57	***
5	13.14	136	d-Limonene	0.22 ± 0.03	0.33 ± 0.06	+0.11	*
6	13.31	136	β-Phellandrene	1.57 ± 0.14	1.42 ± 0.20	−0.15	N
7	13.51	134	p-Cymene	0.07 ± 0.00	0.14 ± 0.02	+0.07	**
8	13.85	136	γ-Terpinene	0.15 ± 0.01	0.29 ± 0.05	+0.14	**
9	14.37	136	Terpinolene	0.29 ± 0.02	0.32 ± 0.04	+0.03	N
10	15.69	150	2-Pentylcyclohexa-1,3-diene	6.00 ± 0.29	6.56 ± 0.52	+0.56	N
11	15.97	148	n-Pentyl-benzene	1.22 ± 0.05	2.12 ± 0.13	+0.90	***
12	17.12	148	C₅-benzene	0.01 ± 0.00	0.13 ± 0.01	+0.12	***
13	17.28	164	1,3,5-Dodecatriene	0.17 ± 0.01	0.20 ± 0.01	+0.03	*
14	17.30	146	1-Phenyl-1-pentene	0.02 ± 0.00	0.20 ± 0.01	+0.18	***
15	17.35	154	α-Terpineol	0.08 ± 0.01	0.12 ± 0.01	+0.04	***
16	18.81	204	α-Copaene	0.20 ± 0.01	0.32 ± 0.03	+0.12	***
17	19.15	196	α-Terpinyl acetate	0.49 ± 0.03	0.44 ± 0.09	−0.05	N
18	19.22	204	β-Elemene	0.44 ± 0.02	0.55 ± 0.06	+0.11	*
19	19.48	152	2,4-Decadienal	0	0.14 ± 0.01	+0.14	**
20	19.54	204	β-Funebrene	0.10 ± 0.01	0.16 ± 0.02	+0.06	***
21	19.68	204	γ-Elemene	0.08 ± 0.01	0.17 ± 0.02	+0.09	***
22	19.83	150	2-Methoxy-4-vinylphenol	0.41 ± 0.09	0.67 ± 0.12	+0.26	**
23	19.91	162	Valerophenone	1.32 ± 0.06	1.77 ± 0.14	+0.45	***
24	20.03	204	α-Bulnesene	0.23 ± 0.01	0.34 ± 0.02	+0.11	***
25	20.40	204	2-Isopropenyl-4a,8-dimethyl-1,2,3,4,4a,5,6,7-octahydronaphthalene	0.12 ± 0.01	0.30 ± 0.03	+0.18	***
26	20.56	204	β-Selinene	1.00 ± 0.06	1.04 ± 0.11	+0.04	N
27	20.63	204	α-Selinene	0.39 ± 0.02	0.41 ± 0.04	+0.02	N
28	20.83	204	δ-Cadinene	0.66 ± 0.04	0.64 ± 0.05	−0.02	N
29	20.95	148	Phthalic anhydride	0.08 ± 0.00	0.85 ± 0.11	+0.77	***
30	21.03	204	α-Gurjunene	0.07 ± 0.01	0.12 ± 0.03	+0.05	**
31	21.09	204	β-Himachalene	0.10 ± 0.01	0.15 ± 0.02	+0.05	**
32	21.12	238	Bornyl isovalerate	0.20 ± 0.02	0.19 ± 0.02	−0.01	N
33	21.24	238	Bornyl pentanoate	0.17 ± 0.01	0.19 ± 0.01	+0.02	N
34	21.51	150	1,3-Cyclohexadiene-1,2-dicarboxylic anhydride	0.77 ± 0.04	0.89 ± 0.08	+0.12	*
35	22.14	222	Elemol	0.28 ± 0.03	0.33 ± 0.05	+0.05	N
36	22.44	222	Carotol	0.13 ± 0.01	0.17 ± 0.02	+0.04	*
37	23.02	222	γ-Eudesmol	0.13 ± 0.01	0.12 ± 0.02	−0.01	N
38	23.10	222	τ-Muurolol	0.25 ± 0.02	0.27 ± 0.05	+0.02	N
39	23.33	222	Unidentified sesquiterpene	0.19 ± 0.01	0.18 ± 0.03	−0.01	N
40	23.40	174	3-Propylidenephthalide	0.15 ± 0.01	0.27 ± 0.04	+0.12	**
41	23.42	222	β-Eudesmol	0.29 ± 0.02	0.24 ± 0.05	−0.05	N
42	23.45	222	Unidentified	0.54 ± 0.05	0.43 ± 0.06	−0.11	*
43	23.50	176	3-Propylphthalide	0.06 ± 0.00	0.33 ± 0.05	+0.27	***
44	24.27	176	(Z)-3-propylidene-4,5-dihydroisobenzofuran-1(3H)-one	1.45 ± 0.12	1.50 ± 0.09	+0.05	N
45	24.49	188	(Z)-3-Butylidenephthalide	4.19 ± 0.30	7.69 ± 0.44	+3.50	***
46	24.56	192	(Z)-Sedanonic acid lactone	0.20 ± 0.04	0.17 ± 0.03	−0.03	N
47	24.61	190	3-n-Butylphthalide	1.04 ± 0.07	1.22 ± 0.08	+0.18	**
48	25.21	192	(E)-Sedanonic acid lactone	0.20 ± 0.01	0.36 ± 0.03	+0.16	***
49	25.26	188	(E)-3-Butylidenephthalide	0.94 ± 0.06	1.42 ± 0.08	+0.48	***
50	25.37	190	(Z)-Ligustilide	58.05 ± 1.90	51.57 ± 2.14	−6.48	**
51	25.47	270	Hexadecanoic acid methyl ester	0	0.20 ± 0.03	+0.20	***
52	25.54	194	3-Butyl-4,5,6,7-tetrahydroisobenzofuran-1(3H)-one	2.07 ± 0.16	2.05 ± 0.10	−0.02	N
53	25.59	218	Isobenzofuranone derivative	0	0.18 ± 0.02	+0.18	***
54	25.65	192	Senkyunolide	1.45 ± 0.09	1.29 ± 0.09	−0.16	*
55	26.09	284	Hexadecanoic acid, ethyl ester	0.42 ± 0.03	0.41 ± 0.04	−0.01	N
56	26.36	190	(E)-Ligustilide	4.06 ± 0.24	5.23 ± 0.22	+1.17	***
57	26.99	186	Ficusin (Furocoumarin)	0.22 ± 0.07	0.21 ± 0.03	−0.01	N
58	27.55	244	Falcarinol	1.02 ± 0.22	0.34 ± 0.10	−0.68	**
59	27.74	218	5-Methoxy-3-butylidenephthalide	0.19 ± 0.01	0.13 ± 0.01	−0.06	***
60	27.83	308	Linoleic acid ethyl ester	0.79 ± 0.07	0.76 ± 0.11	−0.03	N
61	28.47	280	Linoleic acid	0.37 ± 0.25	0	−0.37	*
62	29.47	224	Unidentified	0.75 ± 0.14	0.31 ± 0.11	−0.44	***
63	29.72		Fatty acid ester	1.76 ± 0.35	0	−1.76	***

a p-values (t-test): N, no significant change (p > 0.05);

* 0.05 ≥ p > 0.01;

** 0.01 ≥ p > 0.001;

*** p ≤ 0.001.

Table 2

Relative intensities (area-%) of the compound classes of lovage oil as received (injection) and after Py-GC/MS experiment (pyrolysis).

Compound classes	Injection area-%	Pyrolysis area-%	Difference in area-%
Monoterpenoids	5.05	4.02	−1.03
Alkyl-, alkenyl-benzenes and cyclohexadienes	7.26	9.01	+1.75
Alkyl-, alkenyl- dihydroisobenzofuranones	65.00	59.60	−5.40
Alkyl-, alkenyl-phthalides	6.57	11.06	+4.49
Alkyl-, alkenyl- tetrahydroisobenzofuranones	2.46	2.58	+0.12
Cyclic anhydrides (benzene, cyclohexadiene)	0.86	1.74	+0.88
Sesquiterpenoids	4.46	5.32	+0.86
Fatty acid and alcohol derivatives	4.36	1.71	−2.65
Alkenes and alkenyl oxo compounds	0.17	0.83	+0.66

**Proposed conversion reactions of (Z)-ligustilide during low temperature pyrolysis of lovage oil.** Compound numbers correspond to those in Table 1. The percentage data indicate the change in composition (area-%) (Table 1).

Table 3

Composition of davana oil and pyrolysis products at 300 °C in 9% oxygen / nitrogen atmosphere.

No.	t_ret/min	MW	Compound	Injection /area-% aver. ± std. dev.	Pyrolysis /area-% aver. ± std. dev.	Difference in area-%	Significance level^a
1	9.40	130	Ethyl 2-methylbutanoate	0.20 ± 0.03	0	−0.20	***
2	9.60	130	Ethyl 3-methylbutanoate	0.14 ± 0.02	0	−0.14	***
3	12.04	144	Propyl 2-methylbutanoate	0.29 ± 0.03	0.06 ± 0.04	−0.23	***
4	12.18	144	Propyl 3-methylbutanoate	0.21 ± 0.03	0.03 ± 0.03	−0.18	***
5	13.51	134	p-Cymene	0.41 ± 0.04	0.13 ± 0.09	−0.28	**
6	13.71	106	Benzaldehyde	0.07 ± 0.00	0.18 ± 0.06	+0.11	*
7	15.04	112	5,5-Dimethylfuran-2(5H)-one	0.13 ± 0.01	0.37 ± 0.04	+0.24	***
8	15.16	154	cis-Arbusculone	0	0.12 ± 0.02	+0.12	***
9	15.17	172	2-Methylbutyl 2-methylbutanoate	0.46 ± 0.03	0.23 ± 0.10	−0.23	**
10	15.28	172	2-Methylbutyl pentanoate	0.23 ± 0.01	0.10 ± 0.05	−0.13	**
11	15.54	154	trans-Arbusculone	0.03 ± 0.00	0.20 ± 0.02	+0.17	***
12	15.72	154	Linalool	0.50 ± 0.02	0.28 ± 0.10	−0.22	**
13	16.36	126	5-Ethenyl-5-methyl-dihydrofuran-2(3H)-one	0.13 ± 0.01	0.25 ± 0.03	+0.12	***
14	16.71	138	4-(Propan-2-ylidene) cyclohexanone	0	0.11 ± 0.03	+0.11	***
15	16.88	154	Terpinen-4-ol	0.35 ± 0.01	0.24 ± 0.06	−0.11	*
16	18.18	204	Bicycloelemene (isomer 1)^b	0	0.37 ± 0.04	+0.37	***
17	18.19	182	Nordavanone^b	0.24 ± 0.01	0.31 ± 0.03	+0.07	**
18	18.36	204	Bicycloelemene (isomer 2)	0.18 ± 0.01	2.03 ± 0.10	+1.85	***
19	18.71	164	Methyl 3-phenylpropanoate^b	0	0.12 ± 0.01	+0.12	***
20	18.73	204	Isoledene^b	0.12 ± 0.00	0.04 ± 0.00	−0.08	***
21	18.81	204	α-Copaene	0.17 ± 0.00	0.18 ± 0.02	+0.01	N
22	18.84	210	4-(5-Ethenyl-5-methyltetrahydrofuran-2-yl)pentan-2,3-dione	0.05 ± 0.01	0.37 ± 0.04	+0.32	***
23	19.23	204	β-Elemene	0.52 ± 0.01	0.49 ± 0.04	−0.03	N
		162	Methyl cis-cinnamate +
24	19.28	204	α-Gurjunene +	0.19 ± 0.09	0.34 ± 0.04	+0.15	*
		204	δ-Selinene
25	19.57	196	Geranyl acetate	1.03 ± 0.02	0.82 ± 0.07	−0.21	***
26	19.63	178	Ethyl 3-phenylpropanoate	0.20 ± 0.00	0.19 ± 0.03	−0.01	N
27	19.69	204	β-Caryophyllene	0.33 ± 0.01	0.33 ± 0.02	0	N
28	19.74	204	Eudesma-3,7(11)-diene	0.06 ± 0.01	0.13 ± 0.01	+0.07	***
29	19.82	204	Aromadendrene (isomer 1)	0.75 ± 0.03	0.91 ± 0.06	+0.16	**
30	19.85	204	Eudesma-5,11-diene	0.05 ± 0.00	0.23 ± 0.07	+0.18	**
31	19.90	220	Davana furan	0.70 ± 0.01	0.67 ± 0.05	−0.03	N
32	20.10	192	Benzyl isovalerate^b	0.20 ± 0.03	0.15 ± 0.05	−0.05	N
33	20.12	204	Aromadendrene (isomer 2)^b	0.51 ± 0.08	0	−0.51	***
34	20.15	176	Ethyl cis-cinnamate^b	2.02 ± 0.13	2.45 ± 0.15	+0.43	**
35	20.16	204	α-Humulene^b	0	0.24 ± 0.01	+0.24	***
36	20.28	204	γ-Muurolene	0.13 ± 0.00	0.10 ± 0.02	−0.03	*
37	20.37	162	Methyl trans-cinnamate	1.02 ± 0.02	1.05 ± 0.04	+0.03	N
38	20.45	204	Isobicyclogermacrene	0.23 ± 0.04	0.66 ± 0.14	+0.43	**
39	20.49	204	Ledene	1.27 ± 0.03	1.48 ± 0.06	+0.21	***
40	20.57	204	β-Selinene	2.50 ± 0.05	2.30 ± 0.08	−0.20	**
41	20.76	204	Bicyclogermacrene	11.68 ± 0.10	6.46 ± 0.26	−5.22	***
42	20.81	204	δ-Cadinene +	0.77 ± 0.05	0.96 ± 0.06	+0.19	***
42	20.81	204	γ-Cadinene	0.77 ± 0.05	0.96 ± 0.06	+0.19	***
43	20.96	236	Davanone (isomer 1)^b	0	0.55 ± 0.01	+0.55	***
44	20.97	234	Davana ether (isomer 1)^b	1.94 ± 0.06	1.10 ± 0.03	−0.84	***
45	21.08	190	Precocene	0.04 ± 0.00	0.17 ± 0.02	+0.13	***
46	21.27	234	Davana ether (isomer 2)	5.41 ± 0.20	2.78 ± 0.12	−2.63	***
47	21.34	176	Ethyl trans-cinnamate	6.34 ± 0.14	7.12 ± 0.04	+0.78	***
48	21.45	234	Davana ether (isomer 3)	0.24 ± 0.07	0.16 ± 0.04	−0.08	**
49	21.55	234	Davana ether (isomer 4, 5)	2.84 ± 0.07	1.79 ± 0.11	−1.05	***
50	21.67	224	Geranyl isobutyrate	0.23 ± 0.01	0.16 ± 0.05	−0.07	*
51	21.87	250	Artedouglasia oxide (isomer 1)	0.70 ± 0.02	0.82 ± 0.05	+0.12	**
52	21.95	222	Nerolidol	0.50 ± 0.04	0.45 ± 0.05	−0.05	N
53	22.07	250	Artedouglasia oxide (isomer 2)	0.88 ± 0.03	0.99 ± 0.01	+0.11	***
54	22.11	236	Davanone (isomer 2)	0.50 ± 0.03	0.61 ± 0.05	+0.11	**
55	22.23	236	Davanone (isomer 3)	1.83 ± 0.15	1.69 ± 0.09	−0.14	N
56	22.43	236	Davanone (isomer 4)	1.11 ± 0.02	1.09 ± 0.10	−0.02	N
57	22.53	220	Spathulenol	3.67 ± 0.18	3.90 ± 0.22	+0.23	N
58	22.58	222	Viridiflorol	0.62 ± 0.08	0.95 ± 0.05	+0.33	***
59	22.69	236	(+)-Davanone	29.50 ± 0.63	31.77 ± 1.72	+2.27	*
60	22.87	250	Artedouglasia oxide (isomer 3)	0.26 ± 0.02	0.33 ± 0.03	+0.07	**
61	23.05	222	Cadinol (isomer 1)	1.77 ± 0.03	1.77 ± 0.06	0	N
62	23.17	220	Isospathulenol	0.58 ± 0.05	0.62 ± 0.03	+0.04	N
63	23.32	222	Cadinol (isomer 2) +	0.51 ± 0.02	0.49 ± 0.04	−0.02	N
63	23.32	220	4,8a-Dimethyl-6-(prop-1-en-2-yl)-1,2,3,5,6,7,8,8a-octahydronaphthalen-2-ol	0.51 ± 0.02	0.49 ± 0.04	−0.02	N
64	23.42	222	β-Eudesmol	0.94 ± 0.02	0.99 ± 0.03	+0.05	*
65	23.92	224	Methyl jasmonate	0.28 ± 0.01	0.33 ± 0.03	+0.05	**
66	24.00	202	Desmethoxy encecalin	0.09 ± 0.02	0.20 ± 0.07	+0.11	*
67	24.13	236	Mintsulfide	0.12 ± 0.01	0.18 ± 0.01	+0.06	***
68	24.72	252	2-Hydroxyisodavanone (isomer 1)	0.18 ± 0.02	0.17 ± 0.03	−0.01	N
69	24.81	252	2-Hydroxyisodavanone (isomer 2)	0.19 ± 0.01	0.18 ± 0.03	−0.01	N
70	24.93	252	2-Hydroxyisodavanone (isomer 3)^b	0.14 ± 0.01	0.13 ± 0.01	−0.01	N
71	24.96	268	Hexahydrofarnesyl acetone^b	0.14 ± 0.01	0.18 ± 0.01	+0.04	***
72	25.11	252	2-Hydroxyisodavanone (isomer 4)	1.08 ± 0.03	1.36 ± 0.15	+0.28	**
73	25.14	252	Hydroxyisodavanone	0.16 ± 0.01	0.15 ± 0.03	−0.01	N
74	26.40	296	Heneicosane	0.12 ± 0.01	0.06 ± 0.05	−0.06	N
75	27.50	296	Phytol	0.31 ± 0.03	0	−0.31	***
			29 unidentified peaks	8.68	11.06	+2.38

a p-values (t-test): N, no significant change (p > 0.05);

* 0.05 ≥ p > 0.01;

** 0.01 ≥ p > 0.001;

*** p ≤ 0.001.

b The intensities of the slightly resolved peaks were estimated based on the selected ion chromatograms.

Table 4

Relative intensities (area-%) of the compound classes of davana oil as received (injection) and after Py-GC/MS experiment (pyrolysis).

Compound classes	Injection area-%	Pyrolysis area-%	Difference area-%
Esters	12.56	12.49	−0.07
Bicyclogermacrene	11.68	6.46	−5.22
Other sesquiterpenes	7.59	10.45	+2.86
O-,S-containing sesquiterpenoids	8.09	8.72	+0.63
Davanones	32.95	35.72	+2.77
Hydroxyisodavanones	1.75	2.00	+0.25
Davana ethers	10.43	5.83	−4.60
Other furan derivatives	3.13	4.43	+1.30

**Proposed reactions occurring in davana oil during oxidative pyrolysis.** (a) Conversion of bicyclogermacrene and (b) oxidation reactions of davana ether. Compound numbers correspond to those in Table 3. The percentage data indicate the change in composition (area-%) (Table 3).

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DOI: https://doi.org/10.2478/cttr-2020-0004 | Journal eISSN: 2719-9509 (formerly 1612-9237)

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Language: English, French, German

Page range: 27 - 43

Submitted on: Dec 16, 2019

Accepted on: Mar 30, 2020

Published on: May 23, 2020

Published by: Beiträge zur Tabakforschung GmbH

In partnership with: Paradigm Publishing Services

Keywords:

Flavour,

lovage oil,

davana oil,

gas chromatography/mass spectrometry (GC/MS),

oxidative pyrolysis

Related subjects:

Life sciences,

Life sciences, other

© 2020 Emma Jakab, Zoltán Sebestyén, Bence Babinszki, Eszter Barta-Rajnai, Zsuzsanna Czégény, James Nicol, Peter Clayton, Chuan Liu, published by Beiträge zur Tabakforschung GmbH
This work is licensed under the Creative Commons Attribution-NonCommercial-ShareAlike 4.0 License.

Volume 29 (2020): Issue 1 (April 2020)

Thermo-Oxidative Decomposition of Lovage (Levisticum officinale) and Davana (Artemisia pallens) Essential Oils under Simulated Tobacco Heating Product Conditions

Figures & Tables

Figure 1

Table 1

Table 2

Scheme 1

Figure 2

Table 3

Table 4

Scheme 2

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