Three-dimensional quantitative structure-activity relationship study on gas chromatographic retention index of the fragrance compounds of Liliumspp

doi:10.3724/SP.J.1123.2019.07033

Abstract

Abstract:

Quantitative structure-activity relationship models on the gas chromatographic retention index of the 38 volatile fragrance compounds of Liliumspp were investigated and established by comparative molecular field analysis (CoMFA) and comparative molecular similarity index (CoMSIA) methods. The robustness and predictive performance of the developed models were assessed using external test set validation and leave-one-out cross validation. Further, the effects of the molecular structure on the gas chromatographic retention indices of these compounds were intuitively studied in light of the three-dimensional contour maps of molecular fields provided by the developed CoMSIA and CoMFA models. The validation results demonstrated that both the models could accurately predict the retention indices of the investigated components. The influence of the molecular structure on the retention indices could be reasonably explained by these models. Moreover, the prediction accuracy of the CoMSIA model was slightly higher than that of the CoMFA model. Obviously, the proposed CoMSIA model is more promising for the analysis of the volatile fragrance compounds of Lilium spp.

Key words: gas chromatographic retention index, comparative molecular field analysis (CoMFA), comparative molecular similarity index (CoMSIA), fragrance compounds, liliumspp

JIAO Long, WANG Yuan, TAI Wenliang, LIU Huanhuan, XUE Zhiwei, WANG Yanzhao. Three-dimensional quantitative structure-activity relationship study on gas chromatographic retention index of the fragrance compounds of Liliumspp[J]. Chinese Journal of Chromatography, 2020, 38(5): 600-605.

Figures/Tables 4

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No.	Compound	Experimental RI²⁾	Predicted RI		Relative error/%
No.	Compound	Experimental RI²⁾	CoMFA	CoMSIA	CoMFA	CoMSIA
1) Samples of Group Ⅱ. 2) Compounds 5, 21, 26 are from reference [2] and the rest are from reference [14].
1	α-thujene	931.00	930.85	925.39	-0.02	-0.60
2	5-hepten-2-one, 6-methyl	985.00	984.97	985.66	0.00	0.07
3	myrecene	988.00	989.15	984.84	0.12	-0.32
4	α-phellandrene	1003.00	1003.17	1004.74	0.02	0.17
5¹⁾	2-ethylhexanol	1019.00	1152.07	1068.30	13.06	4.84
6	limonene	1027.00	1026.74	1032.29	-0.03	0.52
7¹⁾	(Z)-ocinene	1036.00	1053.62	1018.19	1.70	-1.72
8	(E)-ocinene	1050.00	1049.68	1053.10	-0.03	0.30
9	1, 3, 8-p-menthatriene	1057.00	1056.28	1058.30	-0.07	0.12
10	phenol-4-methyl	1080.00	1081.50	1077.20	0.14	-0.26
11	γ-terpinolene	1083.00	1082.41	1090.57	-0.05	0.70
12	benzoic acid, methyl ester	1094.00	1093.10	1097.68	-0.08	0.34
13	linalool	1097.00	1096.22	1097.03	-0.07	0.00
14	neo-allo-ocinene	1126.00	1126.11	1131.10	0.01	0.45
15¹⁾	2, 6-dinethyl-1, 3, 5, 7-octatetraene	1128.00	1006.52	1060.52	-10.77	-5.98
16	1-phenyl-1-butene	1145.00	1144.47	1142.51	-0.05	-0.22
17	benzoic acid, ethyl ester	1169.00	1170.02	1169.91	0.09	0.08
18	naphthalene	1182.00	1181.84	1181.45	-0.01	-0.05
19	phenol-2-methoxy-4-methyl	1187.00	1186.67	1183.33	-0.03	-0.31
20	methylsalicylate	1190.00	1190.50	1186.24	0.04	-0.32
21¹⁾	2, 6-dimethyl-2, 4, 6-octatriene	1200.00	1097.95	1241.61	-8.50	3.47
22	benzoic acid, 1-methylethyl ester	1201.00	1263.15	1265.87	5.17	5.40
23¹⁾	trans-carveol	1205.00	1213.05	1153.73	0.67	-4.34
24	geraniol	1249.00	1249.33	1248.28	0.03	-0.06
25	salicylic acid, ethyl ester	1267.00	1266.65	1264.97	-0.03	-0.16
26¹⁾	mesitylene	1290.00	1252.59	1310.29	-2.90	1.57
27	benzoic acid, 2-methylpropyl ester	1325.00	1263.15	1265.87	-4.67	-4.46
28	eugenol	1350.00	1349.84	1348.74	-0.01	-0.09
29¹⁾	benzoic acid, butyl ester	1371.00	1224.26	1321.53	-10.7	-3.61
30	β-elemene	1384.00	1391.97	1389.81	0.58	0.42
31	isoeugenol	1400.00	1391.97	1389.91	-0.57	-0.73
32	longifolene	1404.00	1404.45	1400.67	0.03	-0.24
33	isocaryophillene	1410.00	1409.48	1407.39	-0.04	-0.19
34	α-gurjunene	1414.00	1414.72	1397.42	0.05	-1.17
35¹⁾	α-cedrene	1419.00	1347.40	1352.79	-5.05	-4.67
36	phenol, (E)-2-methoxy-4-(1-propenyl)	1447.00	1447.09	1448.88	0.01	0.13
37	δ-cadinene	1512.00	1511.80	1522.88	-0.01	0.72
38	cedrol	1604.00	1603.74	1609.06	-0.02	0.32

No.	Compound	Experimental RI²⁾	Predicted RI		Relative error/%
No.	Compound	Experimental RI²⁾	CoMFA	CoMSIA	CoMFA	CoMSIA
1) Samples of Group Ⅱ. 2) Compounds 5, 21, 26 are from reference [2] and the rest are from reference [14].
1	α-thujene	931.00	930.85	925.39	-0.02	-0.60
2	5-hepten-2-one, 6-methyl	985.00	984.97	985.66	0.00	0.07
3	myrecene	988.00	989.15	984.84	0.12	-0.32
4	α-phellandrene	1003.00	1003.17	1004.74	0.02	0.17
5¹⁾	2-ethylhexanol	1019.00	1152.07	1068.30	13.06	4.84
6	limonene	1027.00	1026.74	1032.29	-0.03	0.52
7¹⁾	(Z)-ocinene	1036.00	1053.62	1018.19	1.70	-1.72
8	(E)-ocinene	1050.00	1049.68	1053.10	-0.03	0.30
9	1, 3, 8-p-menthatriene	1057.00	1056.28	1058.30	-0.07	0.12
10	phenol-4-methyl	1080.00	1081.50	1077.20	0.14	-0.26
11	γ-terpinolene	1083.00	1082.41	1090.57	-0.05	0.70
12	benzoic acid, methyl ester	1094.00	1093.10	1097.68	-0.08	0.34
13	linalool	1097.00	1096.22	1097.03	-0.07	0.00
14	neo-allo-ocinene	1126.00	1126.11	1131.10	0.01	0.45
15¹⁾	2, 6-dinethyl-1, 3, 5, 7-octatetraene	1128.00	1006.52	1060.52	-10.77	-5.98
16	1-phenyl-1-butene	1145.00	1144.47	1142.51	-0.05	-0.22
17	benzoic acid, ethyl ester	1169.00	1170.02	1169.91	0.09	0.08
18	naphthalene	1182.00	1181.84	1181.45	-0.01	-0.05
19	phenol-2-methoxy-4-methyl	1187.00	1186.67	1183.33	-0.03	-0.31
20	methylsalicylate	1190.00	1190.50	1186.24	0.04	-0.32
21¹⁾	2, 6-dimethyl-2, 4, 6-octatriene	1200.00	1097.95	1241.61	-8.50	3.47
22	benzoic acid, 1-methylethyl ester	1201.00	1263.15	1265.87	5.17	5.40
23¹⁾	trans-carveol	1205.00	1213.05	1153.73	0.67	-4.34
24	geraniol	1249.00	1249.33	1248.28	0.03	-0.06
25	salicylic acid, ethyl ester	1267.00	1266.65	1264.97	-0.03	-0.16
26¹⁾	mesitylene	1290.00	1252.59	1310.29	-2.90	1.57
27	benzoic acid, 2-methylpropyl ester	1325.00	1263.15	1265.87	-4.67	-4.46
28	eugenol	1350.00	1349.84	1348.74	-0.01	-0.09
29¹⁾	benzoic acid, butyl ester	1371.00	1224.26	1321.53	-10.7	-3.61
30	β-elemene	1384.00	1391.97	1389.81	0.58	0.42
31	isoeugenol	1400.00	1391.97	1389.91	-0.57	-0.73
32	longifolene	1404.00	1404.45	1400.67	0.03	-0.24
33	isocaryophillene	1410.00	1409.48	1407.39	-0.04	-0.19
34	α-gurjunene	1414.00	1414.72	1397.42	0.05	-1.17
35¹⁾	α-cedrene	1419.00	1347.40	1352.79	-5.05	-4.67
36	phenol, (E)-2-methoxy-4-(1-propenyl)	1447.00	1447.09	1448.88	0.01	0.13
37	δ-cadinene	1512.00	1511.80	1522.88	-0.01	0.72
38	cedrol	1604.00	1603.74	1609.06	-0.02	0.32

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