HS-SPME/GC-MS法测定北细辛挥发性成分

doi:10.3969/j.issn.1001-1803.2021.11.016

摘要/Abstract

摘要：

建立了北细辛挥发性成分的顶空固相微萃取/气相色谱-质谱法（HS-SPME/GC-MS）分析方法,并对6个不同产地北细辛进行分析,利用谱库检索和保留指数对挥发性成分进行鉴定,从6个产地的北细辛中共鉴定出68种挥发性成分,挥发性成分中甲基丁香酚的相对含量最高,峰面积百分比为17.20%~33.80%。将HS-SPME/GC-MS法应用于北细辛挥发性成分的研究不仅能反映不同产地北细辛挥发性成分的整体差异,且方法简单快速,为北细辛挥发性的质量评价提供新思路。

关键词: 北细辛, 挥发性成分, 顶空固相微萃取/气相色谱-质谱法

Abstract:

Asarum is a kind of commonly used traditional Chinese medicine, and volatile oil is the main material basis for its efficacy. In traditional studies, the volatile oil is extracted by steam distillation and analyzed by GC-MS. Although the extraction method is easy to operate and has low cost, it is time-consuming, large sample consumption, high extraction temperature and easy thermal decomposition of active components. Moreover, xylene is often added in this method to promote the stratification of volatile oil, which brings great interference to the subsequent GC-MS analysis and component identification of volatile oil. Therefore, Solid Phase Microextration （SPME） technology that integrates extraction, purification, enrichment, and sampling functions was used to analyze the volatile oil of Asarum for the first time. The HS-SPME/GC-MS method was established to analyze Asarum heterotropoides, and the volatile components were identified by the NIST spectral library search and retention index. A total of 68 components are identified from the volatile oil of Asarum heterotropoides from 6 origins. The relative content of methyl eugenol is the highest among the volatile components with peak area percentages ranging from 17.20% to 33.80%. The application of HS-SPME/GC-MS method to the study of the volatile components in Asarum heterotropoides can reflect the overall differences, and the method is simple and rapid, providing new ideas for the quality evaluation of Asarum heterotropoides.

Key words: Asarum heterotropoides, volatile components, HS-SPME/GC-MS

中图分类号:

TQ658

王风,李楠,李雪,钟灵艳,黄泽甜,胡坪. HS-SPME/GC-MS法测定北细辛挥发性成分[J]. 日用化学工业, 2021, 51(11): 1150-1157.

Wang Feng,Li Nan,Li Xue,Zhong Lingyan,Huang Zetian,Hu Ping. Analysis of volatile components in Asarum heterotropoides by HS-SPME/GC-MS[J]. China Surfactant Detergent & Cosmetics, 2021, 51(11): 1150-1157.

图/表 6

表 1

图 1

图 2

图 3

图 4

表 2

不同产地的北细辛中挥发性成分鉴定"

类型	t_R/min	化合物	分子式	分子量	匹配度	计算RI	文献RI	峰面积百分比/%
类型	t_R/min	化合物	分子式	分子量	匹配度	计算RI	文献RI	鞍山	靖宇	秦岭	营口	新宾	白山
萜烯烃类	5.45	侧柏烯	C₁₀H₁₆	136	94	927	932	0.02	0.05	0.04	0.05	0.08	0.05
萜烯烃类	5.68	α-蒎烯	C₁₀H₁₆	136	95	933	935	0.18	0.59	0.55	0.46	0.22	0.2
萜烯烃类	6.16	莰烯	C₁₀H₁₆	136	95	946	951	0.07	0.25	0.21	0.18	0.1	0.07
	7.04	桧烯	C₁₀H₁₆	136	92	971	977	0.03	0.18	0.18	0.14	0.05	0.05
	7.15	β-蒎烯	C₁₀H₁₆	136	95	974	980	0.53	1.2	0.76	0.84	0.24	0.51
	7.72	月桂烯	C₁₀H₁₆	136	93	990	992	0.13	0.33	0.19	0.22	0.52	0.4
	8.25	α-水芹烯	C₁₀H₁₆	136	93	1 002	1 005	0.2	0.73	0.56	0.57	1.14	0.54
	8.50	3-蒈烯	C₁₀H₁₆	136	97	1 007	1 010	0.89	1.44	1.04	1.18	1.95	1.73
	8.78	α-松油烯	C₁₀H₁₆	136	93	1 013	1 014	0.03	0.06	0.04	0.04	0.11	0.06
	9.02	邻-异丙基苯	C₁₀H₁₄	134	95	1 018	1 017	0.01	0.01	—	0.01	0.05	0.05
	9.13	4-异丙基甲苯	C₁₀H₁₄	134	94	1 020	1 021	0.31	0.3	0.15	0.33	0.84	1.05
	9.32	柠檬烯	C₁₀H₁₆	136	90	1 024	1 030	0.3	0.61	0.42	0.55	0.82	0.73
	12.27	α-异松油烯	C₁₀H₁₆	136	95	1 085	1 088	0.22	0.55	0.24	0.49	1.37	0.95
	30.68	β-依兰烯	C₁₅H₂₄	204	87	1 379	1 380	0.05	0.05	0.04	0.06	0.04	0.05
	31.09	β-榄香烯	C₁₅H₂₄	204	89	1 384	1 385	0.16	0.14	0.13	0.16	0.14	0.08
	33.94	罗汉柏烯	C₁₅H₂₄	204	93	1 420	1 426	0.3	0.27	0.3	0.27	0.31	0.26
	34.04	β-白菖烯	C₁₅H₂₄	204	93	1 421	1 422	0.84	0.89	0.85	1.09	0.59	0.47
	34.69	檀香烯	C₁₅H₂₄	204	84	1 429	1 427	1.04	1.01	1.12	1.46	0.83	0.71
	34.85	α-愈创烯	C₁₅H₂₄	204	93	1 431	1 433	0.28	0.64	0.62	0.42	0.19	0.13
	35.21	马兜铃烯	C₁₅H₂₄	204	88	1 435	1 429	1.65	1.1	1.05	1.85	0.53	1.02
	36.40	大牛儿烯D	C₁₅H₂₄	204	90	1 449	1 453	0.21	0.22	0.15	0.22	0.09	0.14
	36.81	α-法呢烯	C₁₅H₂₄	204	82	1 453	1 459	—	—	—	—	0.17	0.19
	37.27	β-古巴烯	C₁₅H₂₄	204	88	1 459	NF	1.13	1.27	0.96	1.28	0.29	0.61
	39.05	α-木罗烯	C₁₅H₂₄	204	88	1 479	1 480	0.28	0.41	0.77	0.93	0.1	—
	41.27	δ-愈创木烯	C₁₅H₂₄	204	88	1 505	1 506	0.14	0.2	0.13	0.19	0.09	0.16
	42.43	β-倍半水芹烯	C₁₅H₂₄	204	91	1 517	1 518	0.3	0.37	0.2	0.53	—	0.61
烷烯烃类	25.05	十三烷	C₁₃H₂₈	198	94	1 300	1 300	0.31	0.22	0.17	0.26	0.13	—
	32.07	十四烷	C₁₄H₃₀	198	93	1 400	1 400	0.45	0.41	0.36	0.44	0.51	0.39
	39.36	1-十五烯	C₁₅H₃₀	210	89	1 483	1 489	1.07	1.14	1.22	1.25	0.93	0.63
	41.14	正十五烷	C₁₅H₃₂	240	97	1 500	1 500	19.2	17.7	14	16.6	16.6	13.4
	47.09	3-甲基十五烷	C₁₆H₃₄	296	88	1 567	1 570	0.29	0.21	0.14	0.2	0.27	0.48
	49.93	正十六烷	C₁₆H₃₄	226	86	1 600	1 600	0.27	0.21	0.19	0.21	0.21	0.18
	57.32	8-十七烷烯	C₁₇H₃₄	238	91	1 673	1 670	0.83	0.77	0.65	0.74	0.94	0.88
	59.66	正十七烷	C₁₇H₃₆	240	92	1 700	1 700	1.07	0.74	0.5	0.55	0.59	0.37
醇类	14.79	对薄荷-2,8-二烯-1-醇	C₁₀H₁₆O	152	85	1 131	1 134	0.03	0.02	0.01	0.02	0.03	0.06
	15.10	马鞭草醇	C₁₀H₁₆O	152	86	1 136	1 136	0.13	0.13	0.03	0.11	—	—
	16.51	龙脑	C₁₀H₁₈O	154	96	1 160	1 165	0.86	0.94	1.19	1.05	0.37	0.33
醇类	17.22	4-萜烯醇	C₁₀H₁₈O	154	92	1 172	1 175	0.31	0.33	0.22	0.35	0.27	0.39
	17.75	2- （4-甲基苯基）丙-2-醇	C₁₀H₁₄O	150	90	1 181	1 182	0.14	0.07	0.03	0.12	0.19	0.35
	18.05	α-松油醇	C₁₀H₁₈O	154	94	1 186	1 187	0.36	0.35	0.43	0.42	0.15	0.21
	18.30	桃金娘烯醇	C₁₀H₁₆O	152	81	1 191	1 192	0.02	0.02	0.01	0.02	0.04	0.07
	24.58	麝香草酚	C₁₀H₁₄O	150	88	1 292	1 292	0.08	0.05	0.04	0.05	0.06	0.11
	28.59	丁香酚	C₁₀H₁₂O₂	164	91	1 349	1 353	0.18	0.07	0.2	0.13	0.02	0.1
	46.21	橙花叔醇	C₁₅H₂₆O	222	89	1 557	1 565	0.31	0.24	0.3	0.29	—	—
	52.17	卡枯醇	C₁₀H₁₀O₄	194	82	1 620	NF	2.77	2.2	3.25	2.85	0.03	0.07
	53.15	α-菖蒲醇	C₁₅H₂₆O	222	88	1 630	1 649	0.07	0.03	0.04	0.03	0.01	0.01
	53.49	百秋李醇	C₁₅H₂₆O	222	87	1 634	1 657	0.25	0.44	0.46	0.34	0.11	0.03
酮类	15.25	樟脑	C₁₀H₁₆O	152	96	1 138	1 139	0.17	0.25	0.21	0.22	0.06	0.12
	15.75	优葛缕酮	C₁₀H₁₄O	150	92	1 147	1 243	1.46	1.73	1.56	2.14	6.99	6.79
	19.10	马苄烯酮	C₁₀H₁₄O	150	89	1 204	1 206	0.07	0.11	0.07	0.09	0.06	0.08
	21.92	胡椒酮	C₁₀H₁₈O₂	152	91	1 249	1 250	0.05	0.05	0.03	0.05	0.06	0.09
	23.14	香芹酮	C₁₀H₁₄O	150	86	1 269	1269	0.05	0.1	0.09	0.04	0.04	1.12
	35.77	4’-甲氧基苯丙酮	C₁₀H₁₂O₂	164	92	1 441	NF	0.55	0.6	0.67	0.57	0.14	0.23
	42.90	3,4-（亚甲基二氧代）苯丙酮	C₁₀H₁₀O₃	178	91	1 522	NF	1.73	1.78	3.09	2.18	0.1	0.13
	48.18	3,4-二甲氧基苯丙酮	C₁₁H₁₄O₃	194	82	1 578	NF	0.25	0.21	0.29	0.23	—	—
	55.58	4’,6-二甲基-2-羟基苯乙酮	C₁₀H₁₂O₄	196	82	1 655	1 650	0.21	0.13	0.16	0.1	—	—
	62.41	2’,4’-二甲氧基-3’-甲基苯丙酮	C₁₂H₁₆O₃	208	84	1 605	NF	1.23	1.06	1.31	1.1	—	—
醚类	18.57	草蒿脑	C₁₀H₁₂O	148	96	1 195	1 196	0.82	0.75	0.62	0.91	0.95	1.37
	20.87	百里香酚甲醚	C₁₁H₁₆O	164	93	1 232	1 235	0.21	0.16	0.1	0.14	0.21	0.83
	22.91	3,5-二甲氧基甲苯	C₉H₁₂O₂	152	96	1 265	1 267	5.66	6.59	7.07	5.38	0.78	1.23
	24.36	黄樟醚	C₁₀H₁₀O₂	162	92	1 288	1 289	7.54	8.36	7.7	10.7	0.83	0.84
	33.21	甲基丁香酚	C₁₁H₁₄O₂	178	88	1 412	1 412	20.1	18.6	24	17.2	27.6	33.8
	33.49	3,4,5-三甲氧基甲苯	C₁₀H₁₄O₃	182	86	1 415	1 408	3.74	3.75	3.98	3.8	0.33	0.82
	36.76	2-甲氧基黄樟醚	C₁₁H₁₂O₃	192	88	1 453	1 474	1.88	1.66	0.96	1.88	—	—
	40.16	肉豆蔻醚异构体	C₁₁H₁₂O₃	192	87	1 489	NF	6.61	5.41	3.67	4.98	0.27	0.38
	42.32	肉豆蔻醚	C₁₁H₁₂O₃	192	89	1 513	1 509	0.32	0.39	1.84	0.36	5.11	2.49
	45.90	榄香脂素	C₁₂H₁₆O₃	208	86	1 554	1 558	1.06	1.09	0.83	0.93	16.4	10.2
	47.41	β-细辛醚	C₁₂H₁₆O₃	208	86	1 571	1 596	0.33	0.38	1.01	0.3	0.35	0.34

表 2

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产地	批号	挥发油总量/%（mL·g^-1）
辽宁鞍山	S1	2.25
辽宁鞍山	S2	2.32
吉林靖宇	S3	2.62
吉林靖宇	S4	2.42
辽宁新宾	S5	5.87
辽宁新宾	S6	5.65
吉林白山	S7	3.04
吉林白山	S8	3.00
陕西秦岭	S9	2.18
陕西秦岭	S10	2.26
辽宁营口	S11	2.23
辽宁营口	S12	2.39