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

Jakab, Emma; Sebestyén, Zoltán; Babinszki, Bence; Barta-Rajnai, Eszter; Czégény, Zsuzsanna; Nicol, James; Clayton, Peter; Liu, Chuan

doi:10.2478/cttr-2020-0004

Figures & Tables

(a) GC/MS and (b) Py-GC/MS total ion chromatogram of lovage oil (numbered peak identities are given in Table 1 and are shown in square brackets in the text).

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).

(a) GC/MS and (b) Py-GC/MS total ion chromatogram of davana oil (numbered peak identities are given in Table 3).

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).

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

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

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

Composition of lovage 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	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	***

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

Figures & Tables

Figure 1

Scheme 1

Figure 2

Scheme 2

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

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

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

Composition of lovage oil and pyrolysis products at 300 °C in 9% oxygen / nitrogen atmosphere_

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