气相色谱-质谱法测定化妆品中19种香精香料

doi:10.3969/j.issn.2097-2806.2023.05.013

摘要/Abstract

摘要：

建立了同时测定化妆品中19种香精香料的气相色谱质谱（GC-MS）方法。化妆品样品经甲醇提取，涡旋超声并稀释定容后，以Supelco SLB-5 ms毛细管色谱柱（30 m×250 μm×0. 25 μm）为分离色谱柱进行分析，以电子轰击（EI）源，SIM模式进行质谱监测，外标法定量。19种香精香料在相应的线性范围内线性关系良好，相关系数均大于0.998 0，实验选取了2个不同类型样品进行回收率和精密度的方法学验证实验，19种香精香料在基质①中的加标回收率为88.7%~103.6%，相对标准偏差（RSD，n=6）为1.7%~4.9%；在基质②中的加标回收率为88.4%~102.3%，RSD（n=6）为1.2%~3.9%。实验数据符合相关法律法规及标准要求。该方法实用性较好，定性、定量结果准确、高效，可以用于各类化妆品中香精香料的分析检测，为其提供强有力的技术支撑。

关键词: 气相色谱-质谱法, 香精香料, 化妆品

Abstract:

In this study, methanol was used as the extraction solvent, and gas chromatography-tandem mass spectrometry （GC-MS） was used to detect and analyze 19 kinds of flavors and fragrances by SLB-5 ms capillary column （30 m×250 μm×0.25 μm） within 35 minutes. The selected ion monitoring mode （SIM） scanning measurement was used for separation, and the external standard method was used for quantification. The 19 flavors and fragrances have a good linear relationship within the corresponding linear range, and the correlation coefficients are all greater than 0.998 0. The experimental data meet the requirements of the relevant laws, regulations and standards. At the same time, on the basis of “Safety and Technical Standards for Cosmetics” （2015 edition）, this study has optimized the types of chromatographic columns, mobile phase composition, and sample extraction solvent selection for the determination of 19 flavors and fragrances in cosmetics. Compared with the original method, the stability of the tested substance is better, and the experimental operation is more convenient and efficient. The experimental results show that the research method is fast, simple, reproducible and durable, and the results are accurate and reliable.

Key words: GC-MS, flavors & fragrances, cosmetics

中图分类号:

TQ658

王玮, 邢玉瑾, 张雪. 气相色谱-质谱法测定化妆品中19种香精香料[J]. 日用化学工业（中英文）, 2023, 53(5): 581-587.

Wang Wei, Xing Yujin, Zhang Xue. Determination of 19 flavors and fragrances in cosmetics by gas chromatography-mass spectrometry[J]. China Surfactant Detergent & Cosmetics, 2023, 53(5): 581-587.

图/表 6

图 1

表 1

表 2

表 3

表 4

19种香精香料的加标回收率和相对标准偏差（n=6）"

化合物名称	加标量/（μg/kg）	面霜		乳液
化合物名称	加标量/（μg/kg）	回收率/%	相对标准偏差/%	回收率/%	相对标准偏差/%
（R）-（+）-柠檬烯	5.00	94.5	1.9	94.2	2.5
	25.0	96.7	3.7	97.4	2.4
	50.0	101.6	2.1	100.3	1.6
苯甲醇	5.00	95.1	2.7	92.5	2.8
	25.0	91.4	2.6	95.6	3.6
	50.0	103.6	2.2	102.3	1.7
芳樟醇	5.00	95.9	3.3	93.7	3.0
	25.0	94.4	2.4	94.1	2.8
	50.0	94.8	3.4	92.7	1.2
2-辛炔酸甲酯	5.00	90.8	3.1	91.1	3.0
	25.0	91.1	2.3	89.2	2.9
	50.0	94.3	3.6	86.7	2.1
香茅醇	5.00	91.7	2.2	88.9	1.7
	25.0	92.9	3.7	90.3	1.0
	50.0	92.5	1.9	92.8	2.9
香叶醇	5.00	94.6	2.5	96.5	1.9
	25.0	97.9	2.4	91.7	3.7
	50.0	100.8	1.6	100.6	2.1
羟基香茅醛	5.00	90.5	2.8	91.1	2.7
	25.0	94.6	3.6	91.2	2.6
	50.0	101.3	1.7	103.6	2.2
丁香酚	5.00	92.8	3.0	91.8	3.0
	25.0	92.1	2.3	90.2	2.9
	50.0	93.3	3.9	93.7	2.1
异丁香酚	5.00	95.9	3.3	93.7	3.0
	25.0	94.4	2.4	94.1	2.8
	50.0	94.8	3.4	92.7	1.2
α-异甲基紫罗兰酮	5.00	92.5	2.8	91.1	2.7
	25.0	91.6	3.6	91.2	2.6
	50.0	99.3	1.7	103.6	2.2
丁苯基甲基丙醛	5.00	92.0	3.0	93.8	3.0
	25.0	94.1	2.3	94.2	2.9
	50.0	90.3	3.9	91.7	2.1
戊基肉桂醛	5.00	91.5	1.9	92.2	2.5
	25.0	94.7	3.7	93.4	2.4
	50.0	100.6	2.1	100.3	1.6
羟基异己基-3-环己烯甲醛	5.00	93.1	2.7	93.5	2.8
	25.0	91.4	2.6	90.6	3.6
	50.0	103.6	2.2	99.3	1.7
戊基肉桂醇	5.00	93.9	3.3	93.2	3.0
	25.0	96.4	2.4	94.9	2.8
	50.0	91.8	3.4	92.0	1.2
金合欢醇	5.00	97.6	2.5	93.5	1.9
	25.0	93.9	2.4	95.7	3.7
	50.0	98.8	1.6	99.6	2.1
己基肉桂醛	5.00	90.5	2.8	91.1	2.7
	25.0	89.6	3.6	89.2	2.6
	50.0	89.3	1.7	91.6	2.2
苯甲酸苄酯	5.00	90.8	3.0	91.8	3.0
	25.0	93.1	2.3	90.2	2.9
	50.0	90.3	3.9	91.7	2.1
水杨酸苄酯	5.00	91.8	3.4	92.0	1.2
	25.0	97.6	2.5	93.5	1.9
	50.0	93.9	2.4	95.7	3.7
肉桂酸苄酯	5.00	88.7	1.6	90.6	2.1
	25.0	89.7	2.8	91.1	2.7
	50.0	89.6	3.6	89.2	2.6

表 4

表 5

参考文献 15

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化合物名称	保留时间/min	定量离子/ （m/z）	定性离子1/ （m/z）	定性离子2/ （m/z）
（R）-（+）-柠檬烯	5.359	68	93	67
苯甲醇	5.37	108	79	107
芳樟醇	6.781	71	93	55
2-辛炔酸甲酯	9.182	95	123	55
香茅醇	9.887	69	41	67
香叶醇	10.5	69	41	68
羟基香茅醛	11.416	59	43	71
丁香酚	13.136	164	77	103
异丁香酚	15.524	164	77	149
α-异甲基紫罗兰酮	16.191	135	150	107
丁苯基甲基丙醛	17.459	189	147	131
戊基肉桂醛	20.209	117	129	91
羟基异己基-3-环己烯甲醛	20.638	136	79	59
戊基肉桂醇	21.061	91	133	115
金合欢醇	21.248；21.768	69	41	81
己基肉桂醛	22.409	129	117	91
苯甲酸苄酯	22.878	105	91	77
水杨酸苄酯	25.021	91	65	228
肉桂酸苄酯	29.384	91	131	192

化合物名称	回收率/%
化合物名称	甲醇	二氯甲烷	四氢呋喃	乙腈	正己烷	丙酮
（R）-（+）-柠檬烯	94.1	82.4	86.0	92.5	68.5	90.1
苯甲醇	96.1	88.8	90.7	92.8	67.3	101.2
芳樟醇	93.7	87.3	88.4	93.5	68.8	94.9
2-辛炔酸甲酯	90.1	87.4	89.6	94.4	63.3	92.7
香茅醇	96.0	87.8	88.9	94.5	70.6	96.6
香叶醇	99.5	93.9	92.8	93.4	75.3	100.3
羟基香茅醛	93.4	76.2	77.2	89.9	77.0	85.2
丁香酚	92.3	85.5	100.4	91.3	67.2	85.0
异丁香酚	93.7	97.5	92.7	98.3	62.4	83.4
α-异甲基紫罗兰酮	93.2	83.2	90.2	96.1	67.8	89.7
丁苯基甲基丙醛	98.5	93.3	93.5	98.1	74.9	91.6
戊基肉桂醛	99.7	89.1	96.7	92.2	66.9	93.6
羟基异己基-3-环己烯甲醛	100.5	94.0	95.1	92.8	71.4	100.2
戊基肉桂醇	91.3	88.7	90.3	90.2	68.3	88.2
金合欢醇	95.2	93.8	91.1	92.4	66.9	90.4
己基肉桂醛	95.1	94.1	78.9	83.5	70.3	89.5
苯甲酸苄酯	94.2	88.5	88.3	80.7	72.9	93.1
水杨酸苄酯	93.5	87.0	90.6	82.5	71.5	92.4
肉桂酸苄酯	94.2	90.3	88.3	90.7	69.7	90.3
平均回收率/%	95.0	88.9	89.9	91.6	69.5	92.0

化合物名称	线性范围/（mg/L）	线性方程	相关系数R²	检出限/（mg/kg）	定量限/（mg/kg）
（R）-（+）-柠檬烯	1~50	Y=1.11×10⁵X+4.568×10⁴	0.999 5	0.10	0.30
苯甲醇	1~50	Y=1.04×10⁵X+1.289×10⁵	0.998 9	0.10	0.30
芳樟醇	1~50	Y=8.11×10⁴X-2.206×10³	0.999 7	0.18	0.54
2-辛炔酸甲酯	1~50	Y=4.71×10⁴X+1.416×10⁴	0.998 6	0.22	0.66
香茅醇	1~50	Y=7.34×10⁴X+5.665×10⁴	0.999 7	0.30	0.90
香叶醇	1~50	Y=1.25×10⁵X-1.247×10⁵	0.999 4	0.25	0.75
羟基香茅醛	5~50	Y=1.03×10⁵X-1.252×10⁵	0.999 3	0.41	1.23
丁香酚	1~50	Y=5.80×10⁴X-1.238×10⁵	0.997 3	0.45	1.35
异丁香酚	1~50	Y=6.16×10⁴X-1.482×10⁵	0.996 1	0.33	0.99
α-异甲基紫罗兰酮	1~50	Y=1.76×10⁵X-1.01×10⁵	0.999 5	0.50	1.50
丁苯基甲基丙醛	1~50	Y=1.16×10⁵X-1.26×10⁵	0.999 5	0.15	0.45
戊基肉桂醛	1~50	Y=5.02×10⁴X-4.74×10⁵	0.999 2	0.25	0.75
羟基异己基-3-环己烯甲醛	1~50	Y=2.13×10⁴X-4.74×10⁴	0.996 7	0.40	1.20
戊基肉桂醇	1~50	Y=5.91×10⁴X-1.33×10⁵	0.997 1	0.55	1.65
金合欢醇	1~50	Y=8.14×10⁴X-1.59×10⁴	0.997 1	0.60	1.80
己基肉桂醛	1~50	Y=5.79×10⁴X-5.56×10⁴	0.998 9	0.35	1.05
苯甲酸苄酯	1~50	Y=2.04×10⁵X-1.02×10⁵	0.999 2	0.45	1.35
水杨酸苄酯	1~50	Y=1.88×10⁵X-8.15×10⁵	0.993 7	0.55	1.65
肉桂酸苄酯	1~50	Y=8.92×10⁴X-2.10×10⁵	0.996 9	0.60	1.80

化合物名称	面霜		乳液
化合物名称	样品1/%	样品2/%	样品1/%	样品2/%
（R）-（+）-柠檬烯	1.3	2.6	ND	ND
苯甲醇	ND	ND	3.7	3.9
芳樟醇	2.66	2.97	3.96	4.15
2-辛炔酸甲酯	ND	ND	ND	ND
香茅醇	ND	ND	ND	ND
香叶醇	ND	ND	4.33	3.98
羟基香茅醛	ND	ND	ND	ND
丁香酚	3.98	4.53	0.88	1.02
异丁香酚	ND	ND	ND	ND
α-异甲基紫罗兰酮	ND	ND	ND	ND
丁苯基甲基丙醛	4.55	5.01	2.34	5.12
戊基肉桂醛	ND	ND	ND	ND
羟基异己基-3-环己烯甲醛	3.87	4.53	ND	ND
戊基肉桂醇	ND	ND	5.11	5.25
金合欢醇	2.98	2.77	ND	ND
己基肉桂醛	ND	3.11	3.45	ND
苯甲酸苄酯	4.26	ND	ND	4.44
水杨酸苄酯	1.98	4.89	3.83	2.79
肉桂酸苄酯	ND	4.99	ND	3.63