基质固相分散-气相色谱质谱联用法测定沉香中精油的化学成分

doi:10.3969/j.issn.0253-2417.2021.03.007

Abstract

Abstract:

Matrix solid-phase dispersion-gas chromatography combined with mass spectrometry(MSPD-GC/MS) analysis method for essential oil was established based on Hainan agarwood induced by biotechnological method. The MSPD conditions of extracting agarwood essential oil established by single factor test were magnesium silicate as the adsorbent, adsorbent/sample mass ratio 4:1, isopropanol as the dispersion solvent, dispersion solvent/sample ratio 4:1(mL: g) and 6 mL n-hexane/ethyl acetate 9:1(volume ratio) as the elution solvent. Under these conditions, the extraction yield of MSPD was (9.19±0.15)%, which was higher than ultrasonic assisted ether extraction (6.65±0.22)%. The chemical constituents of essential oil were analysis by GC/MS, and compared with that extracted by ultrasonic assisted ether extraction. The compositions of essential oil extracted by MSPD were similar to ultrasonic assisted ether extraction, the main constituents were 2.13% aromatic, 25.67% sesquiterpenoids, 26.85% chromones and 7.50% aliphatic compounds. The number of sesquiterpenoids in the essential oil extracted by MSPD was more than that of ultrasonic assisted ether extraction, such as γ-selinene, β-santalol, valerena-4, 7(11)-diene, α-guaiene, shyobunol and 1, 9-aristo-ladiene. Thus, the MSPD-GC/MS analysis method could truly reflect the chemical composition of agarwood essential oil, which could be used as a rapid identification method for the quality evaluation of agarwood.

Key words: agarwood, essential oil, matrix solid-phase dispersion, GC-MS, chemical constituents

CLC Number:

TQ35

Hongxia CHEN, Hao ZHOU, Jianzhong YE, Ran TAO, Wenjun LI, Chengzhang WANG. Matrix Solid-phase Dispersion Combined with GC-MS for Determination of Chemical Constituents of Essential Oil in Agarwood[J]. Chemistry and Industry of Forest Products, 2021, 41(3): 47-54.

Figures/Tables 3

Table 1

Fig.1

Table 2

Chemical constituents of essential oil in agarwood extracted by different methods"

编号 No.	出峰时间/min peak time	化合物 compound	分子式 molecular formula	M_r	相对峰面积relative area/%
编号 No.	出峰时间/min peak time	化合物 compound	分子式 molecular formula	M_r	基质固相分散提取 matrix solid-phase dispersion	乙醚超声波提取 ultrasonic assisted ether extraction
1	19.493	苄基丙酮4-phenyl-2-butanone	C₁₀H₁₂O	148	0.49	—
2	29.323	2, 6-二叔丁基对甲苯酚 2, 6-di-tert-butyl-4-methylpheno	C₁₅H₂₄O	220	0.13	0.24
3	29.513	γ-芹子烯γ-selinene	C₁₅H₂₄	204	0.29	—
4	29.954	β-芹子烯β-selinene	C₁₅H₂₄	204	0.50	0.46
5	30.208	巴伦西亚橘烯valencene	C₁₅H₂₄	204	0.44	0.56
6	30.338	愈创木脂-9, 11-二烯guaia-9, 11-diene	C₁₅H₂₄	204	0.40	0.45
7	32.415	(3R, 8aR)-5, 8a-二甲基-3-(丙-1-烯-2-基)-1, 2, 3, 7, 8, 8a-六氢萘 (3R, 8aR)-5, 8a-dimethyl-3-(prop-1-en-2-yl)-1, 2, 3, 7, 8, 8a-hexahydronaphthalene	C₁₅H₂₂	202	1.14	0.93
8	33.899	β-檀香醇β-santalol	C₁₅H₂₄O	220	0.38	—
9	34.062	β-乙位香根烯β-vetivenen	C₁₅H₂₂	202	0.30	0.33
10	35.247	缬草-4, 7(11)二烯valerena-4, 7(11)-diene	C₁₅H₂₄	204	0.28	—
11	35.452	γ-马阿里烯γ-maaliene	C₁₅H₂₄	204	0.60	0.66
12	35.544	α-姜黄烯α-curcumene	C₁₅H₂₂	202	0.62	0.49
13	35.974	(+)-γ-桉叶醇(+)-γ-eudesmol	C₁₅H₂₆O	222	0.63	0.89
14	36.141	沉香螺旋醇agarospirol	C₁₅H₂₆O	222	1.43	0.80
15	36.272	茅苍术醇hinesol	C₁₅H₂₆O	222	—	0.65
16	36.429	揽香醇elemol	C₁₅H₂₆O	222	0.94	0.81
17	36.706	(4aR, 8aR)-2-异亚丙基-4a, 8-二甲基-1, 2, 3, 4, 4a, 5, 6, 8a-八氢萘 (4aR, 8aR)-2-isopropylidene-4a, 8-dimethyl-1, 2, 3, 4, 4a, 5, 6, 8a-octahydronaphtalene	C₁₅H₂₄	204	1.74	1.90
18	36.814	白菖烯(+)-calarene	C₁₅H₂₄	204	2.93	2.94
19	37.238	α-愈创木烯α-guaiene	C₁₅H₂₄	204	0.41	—
20	38.476	(+)-香橙烯(+)-aromandendrene	C₁₅H₂₄	204	0.54	0.45
21	38.599	(2R)-1, 2, 3, 4, 4a, 5, 6, 8aβ-八氢-4aα, 8-二甲基-α-亚甲基-2-萘乙醛 (2R)-1, 2, 3, 4, 4a, 5, 6, 8aβ-octahydro-4aα, 8-dimethyl-α-methylene-2-naphthaleneacetaldehyde	C₁₅H₂₂O	218	0.81	0.35
22	39.203	异香橙烯环氧化物isoaromadendrene epoxide	C₁₅H₂₄O	220	0.64	0.74
23	39.630	(-)-异长叶醇(-)-isolongifolol	C₁₅H₂₆O	222	0.92	0.72
24	40.492	百里香酚thymol	C₁₀H₁₄O	150	1.21	1.12
25	40.677	白菖醇shyobunol	C₁₅H₂₆O	222	0.34	—
26	41.036	1, 9-马兜铃二烯1, 9-aristo-ladiene	C₁₅H₂₂	202	0.47	—
27	41.393	(-)-柳杉二醇(-)-cryptomeridiol	C₁₅H₂₈O₂	240	1.04	1.00
28	42.422	艾里莫芬-7(11), 9-二烯-8-酮 eremophila-7(11), 9-dien-8-one	C₁₅H₂₂O	218	2.03	1.74
29	42.849	缬草酸valerenic acid	C₁₅H₂₂O₂	234	0.29	—
30	43.837	cis-β-愈创木烯cis-β-guaiene	C₁₅H₂₄	204	0.59	0.37
31	44.073	香树烯(-)-alloaromadendrene	C₁₅H₂₄	204	0.49	—
32	45.283	6, 9-十八碳二炔酸甲酯 6, 9-octadecadiynoic acid, methyl ester	C₁₉H₃₀O₂	290	1.05	0.36
33	45.486	木香醇costol	C₁₅H₂₄O	220	—	0.97
34	47.787	长叶烯longifolene	C₁₅H₂₄	204	3.27	4.14
35	48.511	绒白乳菇醛velleral	C₁₅H₂₀O₂	232	4.53	3.94
36	48.878	棕榈酸乙酯ethyl palmitate	C₁₈H₃₆O₂	284	1.11	1.79
37	49.032	二十烷eicosane	C₂₀H₄₂	282	0.63	1.38
38	49.907	1, 5-二苯基-3-戊酮1, 5-diphenyl-3-pentanone	C₁₇H₁₈O	238	0.37	—
39	51.355	喘诺木烯内酯reynosin	C₁₅H₂₀O₃	248	0.36	0.29
40	51.992	亚油酸甲酯methyl octadeca-9, 12-dienoate	C₁₉H₃₄O₂	294	0.64	—
41	52.122	正二十一烷heneicosane	C₂₁H₄₄	296	1.12	2.74
42	52.171	反9-十八碳烯酸甲酯 methyl 9-(Z)-octadecenoate	C₁₉H₃₆O₂	296	1.61	—
43	52.886	10-甲基十七烷酸甲酯 methyl 10-methylheptadecanoate	C₁₉H₃₈O₂	298	0.09	—
44	54.683	二十四烷tetracosane	C₂₄H₅₀	338	0.74	2.59
45	56.927	三十一烷hentriacontane	C₃₁H₆₄	436	0.51	1.33
46	57.918	2-(2-苯乙基)色酮2-(2-phenylethyl)chromone	C₁₇H₁₄O₂	250	7.96	8.61
47	59.528	2, 2′-亚甲基双-(4-甲基-6-叔丁基苯酚) 2, 2′-methylenebis(6-tert-butyl-4-methylphenol)	C₂₃H₃₂O₂	340	1.14	3.44
48	60.728	(E)-14-十六烷烯醛(E)-14-hexadecenal	C₁₆H₃₀O	238	—	0.44
49	62.469	山嵛酸乙酯ethyl behenate	C₂₄H₄₈O₂	368	—	0.44
50	62.856	6-甲氧基-2-苯乙基色酮 6-methoxy-2-phenethyl-4H-chromen-4-one	C₁₈H₁₆O₃	280	7.44	8.69
51	65.524	芥酸酰胺13-docosenamide	C₂₂H₄₃NO	337	—	0.31
52	66.156	角鲨烯squalene	C₃₀H₅₀	410	—	2.31
53	67.301	6, 7-二甲氧基-2-(苯基乙基)色酮 6, 7-dimethoxy-2-(2-phenylethyl)chromen-4-one	C₁₉H₁₈O₄	310	10.49	14.74
54	72.648	6, 7-二甲氧基-2-[2-(4-甲氧基苯基)乙基]色酮 6, 7-dimethoxy-2-(2-(4-methoxyphenyl)ethyl)chromone	C₂₀H₂₀O₅	340	0.96	0.79
鉴定出化合物的总量total content of the identified compounds					67.04	77.90
芳香族化合物的总量total content of aromatic compounds					2.13	3.68
倍半萜类化合物的总量total content of sesquiterpenoids					25.67	25.78
色酮类化合物的总量total content of chromones					26.85	32.83
脂肪族化合物的总量total content of aliphatic compounds					7.50	11.38

Table 2

References 25

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条件 conditions		峰面积peak area
条件 conditions		苄基丙酮 4-phenyl-2-butanone	檀香醇 santalol	2-(2-苯乙基)色酮 2-(2-phenylethyl)chromone
吸附基质 adsorbent	C₁₈	199181	167452	2858862
	C₈	191218	196660	3287237
	沙子sand	60697	114892	1966072
	硅藻土diatomite	164125	190703	3473300
	硅胶silica gel	127754	147649	2602214
	硅酸镁magnesium silicate	228715	237310	3355021
	石英沙quartz sand	40332	79827	1236267
吸附基质与样品质量比 mass ratio of sample to adsorbent	1∶1	71020	132748	2006192
	2∶1	154637	163910	2936471
	3∶1	181270	170772	2742589
	4∶1	228715	237310	3355021
	5∶1	202770	179297	3037831
分散溶剂 dispersion solvent	甲醇methanol	15318	164315	2248841
	乙醇ethanol	180359	269464	3659811
	正丙醇n-propyl alcohol	228715	237310	3355021
	异丙醇isopropanol	284209	234216	3656676
	1, 4-二氧六环1, 4-dioxane	213957	222755	3332400
分散溶剂与样品比(mL∶g) sample to dispersing liquid ratio	1∶1	72544	199057	2292822
	2∶1	121426	236120	3038727
	3∶1	164838	236437	3158548
	4∶1	228715	237310	3355021
	5∶1	232706	236264	3180245
	6∶1	230696	169621	3183128
洗脱溶剂用量 volume of eulution solvent	2 mL	48790	71258	942311
	4 mL	128642	142198	1797259
	6 mL	221778	230090	3303776
	8 mL	227331	237017	3319090
	10 mL	228715	237310	3355021

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Matrix Solid-phase Dispersion Combined with GC-MS for Determination of Chemical Constituents of Essential Oil in Agarwood

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