基于顶空-气相-离子迁移谱和顶空-气相-质谱技术的化妆品真伪性鉴别研究

doi:10.3969/j.issn.2097-2806.2026.06.014

Abstract

Abstract:

Focusing on toner, lotion and cream matrices, the fingerprints of volatile organic compounds were constructed to characterize the differences among various cosmetics, and achieve accurate authenticity identification. A combined approach utilizing headspace-gas chromatography-ion mobility spectrometry （HS-GC-IMS） and headspace-gas chromatography-mass spectrometry （HS-GC-MS） technologies was used to detect differences between genuine and counterfeit cosmetics. The HS-GC-IMS spectra were processed using the built-in NIST and IMS databases to reveal 91, 37, and 37 active ingredients, respectively, from which 83, 30, and 23 compounds are identified. The Gallery Plot plugin was used for fingerprint analysis; the similarity results show that the similarities for genuine products are greater than 85%, 93%, and 91%, respectively, while those for the counterfeit products are less than 64%, 31%, and 43%, respectively. Furthermore, HS-GC-IMS data were analyzed using the traditional Chinese medicine chromatographic fingerprint similarity evaluation system based on total ion chromatogram data. The similarity between genuine products ranged from 0.968 to 0.999, while those between counterfeit products range from 0.003 to 0.849. Both methods proved highly effective in distinguishing between genuine and counterfeit cosmetics. Therefore, the combination of HS-GC-MS and HS-GC-IMS technologies can be successfully applied to the comparative analysis of organic volatile components in genuine and counterfeit cosmetics, enabling rapid and accurate authentication, and providing scientific basis for cosmetic authenticity authentication studies.

Key words: cosmetics, headspace-gas chromatography-ion mobility spectrometry, headspace-gas chromatography-mass spectrometry, volatile organic compounds, authenticity identification

CLC Number:

TQ658

Liqiong Gao, Guofang Shen, Wei Zhang, Xiuxiu Wang, Yue Xu, Xia Wang. Authenticity identification of cosmetics based on headspace-gas chromatography-ion mobility spectrometry and headspace-gas chromatography-mass spectrometry technologies[J].China Surfactant Detergent & Cosmetics, 2026, 56(6): 811-820.

Figures/Tables 16

Tab.1

Fig.1

Fig.2

Fig.3

Tab.2

Identification of volatile organic compounds in essence by GC-IMS"

编号	化合物	CAS号	分子式	分子量	保留指数	保留时间/sec	相对迁移时间/RIP ral.	备注
1	2-羟基-4-甲基戊酸乙酯	10348-47-7	C₈H₁₆O₃	160.2	1 071.9	889.7	1.866	D
2	庚酸乙酯	106-30-9	C₉H₁₈O₂	158.2	1 094.2	944.3	1.924
3	薄荷脑	89-78-1	C₁₀H₂₀O	156.3	1 178.2	1 183.0	1.866
4	辛酸	124-07-2	C₈H₁₆O₂	144.2	1 196.0	1 240.9	1.872
5	2-氨基吡啶	504-29-0	C₅H₆N₂	94.1	1 000.4	734.4	1.786
6	2-乙基己醇	104-76-7	C₈H₁₈O	130.2	1 029.5	794.0	1.409
7	4-叔丁基苯酚	98-54-4	C₁₀H₁₄O	150.2	1 304.2	1 659.0	1.478
8	异戊酸乙酯	108-64-5	C₇H₁₄O₂	130.2	1 196.7	1 243.4	1.254
9	氧化异佛尔酮	10276-21-8	C₉H₁₄O₂	154.2	1 195.9	1 240.5	1.334
10	二乙基三硫醚	3600-24-6	C₄H₁₀S₃	154.3	1 133.1	1 048.3	1.242
11	反式-2-壬醛	18829-56-6	C₉H₁₆O	140.2	1 165.4	1 143.1	1.398	M
12	反式-2-壬醛	18829-56-6	C₉H₁₆O	140.2	1 153.8	1 108.1	1.962	D
13	壬醛	124-19-6	C₉H₁₈O	142.2	1 106.1	975.1	1.457
14	玫瑰醚	16409-43-1	C₁₀H₁₈O	154.3	1 094.0	943.9	1.348
15	正庚醇	111-70-6	C₇H₁₆O	116.2	968.7	663.7	1.747
16	二异丁基酮	108-83-8	C₉H₁₈O	142.2	967.1	660.2	1.804
17	丁酸异丁酯	539-90-2	C₈H₁₆O₂	144.2	951.3	627.2	1.804
18	苯甲醇	100-51-6	C₇H₈O	108.1	1 028.6	791.9	1.326	M
19	异戊酸丁酯	109-19-3	C₉H₁₈O₂	158.2	1 057.1	854.9	1.906
20	3-蒈烯	13466-78-9	C₁₀H₁₆	136.2	1 014.7	762.9	2.214	D
21	正戊酸正戊酯	2173-56-0	C₁₀H₂₀O₂	172.3	1 160.5	1 128.1	2.027
22	异丁酸己酯	2349-07-7	C₁₀H₂₀O₂	172.3	1 106.4	975.8	2.068
23	乙酸反-2-己烯酯	2497-18-9	C₈H₁₄O₂	142.2	1 006.8	747.1	1.860
24	β-蒎烯	127-91-3	C₁₀H₁₆	136.2	975.3	678.2	1.626
25	庚酸	111-14-8	C₇H₁₄O₂	130.2	1 071.0	887.4	1.357
26	反-2-辛烯醛	2548-87-0	C₈H₁₄O	126.2	1 055.1	850.3	1.331
27	2-甲基丁酸丁酯	15706-73-7	C₉H₁₈O₂	158.2	1 043.5	824.4	1.375
28	N-甲基吡咯烷酮	872-50-4	C₅H₉NO	99.1	1 037.6	811.3	1.442
29	3-蒈烯	13466-78-9	C₁₀H₁₆	136.2	1 013.0	759.5	1.725	M
30	乙酸己酯	142-92-7	C₈H₁₆O₂	144.2	1 009.5	752.5	1.395
31	苯甲醇	100-51-6	C₇H₈O	108.1	1 025.0	784.5	1.769	D
32	罗勒烯	13877-91-3	C₁₀H₁₆	136.2	1 025.7	785.8	1.705	D
33	罗勒烯	13877-91-3	C₁₀H₁₆	136.2	1 025.9	786.3	1.249	M
34	2-正戊基呋喃	3777-69-3	C₉H₁₄O	138.2	994.9	722.9	1.244
35	2-甲基戊酸	97-61-0	C₆H₁₂O₂	116.2	999.5	732.6	1.273
36	四氢噻吩-3-酮	1003-04-9	C₄H₆OS	102.2	975.2	677.9	1.429
37	3-甲基-2- （5H） -呋喃酮	22122-36-7	C₅H₆O₂	98.1	983.2	695.9	1.370
38	己酸	142-62-1	C₆H₁₂O₂	116.2	986.6	703.6	1.302
39	正丙苯	103-65-1	C₉H₁₂	120.2	955.4	635.7	1.244
40	丁酸异丁酯	539-90-2	C₈H₁₆O₂	144.2	959.7	644.6	1.339
41	γ-戊内酯	108-29-2	C₅H₈O₂	100.1	961.5	648.3	1.132
42	二丁醚	142-96-1	C₈H₁₈O	130.2	940.1	604.7	1.721
43	3-庚醇	589-82-2	C₇H₁₆O	116.2	897.4	526.1	1.656
44	2-甲基丁基乙酸酯	624-41-9	C₇H₁₄O₂	130.2	880.0	492.4	1.732	D
45	2-甲基丁基乙酸酯	624-41-9	C₇H₁₄O₂	130.2	879.8	491.9	1.287	M
46	2, 6-二甲基吡嗪	108-50-9	C₆H₈N₂	108.1	897.4	526.1	1.537	M
47	正戊酸	109-52-4	C₅H₁₀O₂	102.1	888.5	509.5	1.492
48	3-庚酮	106-35-4	C₇H₁₄O	114.2	873.9	480.2	1.600
49	4-庚酮	123-19-3	C₇H₁₄O	114.2	863.3	459.9	1.591
50	2-甲基-1-丁醇	105-30-6	C₆H₁₄O	102.2	850.8	437.2	1.580
51	巴豆酸乙酯	623-70-1	C₆H₁₀O₂	114.1	843.9	425.1	1.559
52	反式-2-己烯醛	6728-26-3	C₆H₁₀O	98.1	851.1	437.6	1.520
53	2-甲基-2-戊烯醛	623-36-9	C₆H₁₀O	98.1	843.2	423.9	1.504
54	乙酸异戊酯	123-92-2	C₇H₁₄O₂	130.2	864.8	462.8	1.763
55	2, 4-二甲基-1-庚烯	19549-87-2	C₉H₁₈	126.2	851.7	438.7	1.726
56	丁酸异丙基酯	638-11-9	C₇H₁₄O₂	130.2	843.8	424.9	1.691
57	乙酸丁酯	123-86-4	C₆H₁₂O₂	116.2	828.3	399.0	1.614
58	乳酸乙酯	97-64-3	C₅H₁₀O₃	118.1	812.9	374.7	1.535
59	甲酸戊酯	638-49-3	C₆H₁₂O₂	116.2	805.3	363.3	1.653
60	乙酸异丁酯	110-19-0	C₆H₁₂O₂	116.2	767.8	311.5	1.612
61	2-甲基戊醛	123-15-9	C₆H₁₂O	100.2	743.6	281.8	1.530
62	硫氰酸甲酯	556-64-9	C₂H₃NS	73.1	717.8	253.1	1.361
63	丁酸甲酯	623-42-7	C₅H₁₀O₂	102.1	719.0	254.4	1.446
64	甲酸丁酯	592-84-7	C₅H₁₀O₂	102.1	729.5	265.7	1.514
65	2, 6-二甲基吡嗪	108-50-9	C₆H₈N₂	108.1	898.6	528.3	1.135	D
66	正戊醛	110-62-3	C₅H₁₀O	86.1	708.1	243.2	1.183
67	2-戊醇	6032-29-7	C₅H₁₂O	88.1	689.7	225.3	1.209
68	羟基丙酮	116-09-6	C₃H₆O₂	74.1	640.2	189.3	1.225	D
69	羟基丙酮	116-09-6	C₃H₆O₂	74.1	635.5	186.2	1.053	M
70	异戊醛	590-86-3	C₅H₁₀O	86.1	655.7	199.9	1.407
71	正丁醛	123-72-8	C₄H₈O	72.1	587.7	157.6	1.277
72	丁酸	107-92-6	C₄H₈O₂	88.1	821.7	388.4	1.158
73	1-辛烯	111-66-0	C₈H₁₆	112.2	797.9	352.6	1.172	M
74	1-辛烯	111-66-0	C₈H₁₆	112.2	794.9	348.3	1.466	D
75	3-甲基-2-丁烯醛	107-86-8	C₅H₈O	84.1	754.8	295.1	1.365	D
76	3-甲基-2-丁烯醛	107-86-8	C₅H₈O	84.1	756.8	297.6	1.098	M
77	二丁基硫醚	544-40-1	C₈H₁₈S	146.3	1 081.2	912.1	1.306
78	二甲基三硫	3658-80-8	C₂H₆S₃	126.3	945.6	615.7	1.314
79	乙二醇丁醚醋酸酯	112-07-2	C₈H₁₆O₃	160.2	853.2	441.4	1.283
80	糠（基）硫醇	98-02-2	C₅H₆OS	114.2	913.2	553.9	1.345
81	1-戊烯-3-醇	616-25-1	C₅H₁₀O	86.1	666.7	207.7	1.348
82	1-丙硫醇	107-03-9	C₃H₈S	76.2	611.4	171.2	1.369	D
83	1-丙硫醇	107-03-9	C₃H₈S	76.2	626.0	180.1	1.184	M

Tab.2

Tab.3

Identification of volatile organic compounds in primer by GC-IMS"

编号	化合物	CAS号	分子式	分子量	保留指数	保留时间/sec	相对迁移时间/RIP ral.	备注
1	反式-2-壬烯醛	18829-56-6	C₉H₁₆O	140.2	1 236.6	1 352.1	1.971
2	2-甲基戊酸乙酯	39255-32-8	C₈H₁₆O₂	144.2	1 085.6	923.9	1.750	D
3	2-甲基戊酸乙酯	39255-32-8	C₈H₁₆O₂	144.2	1 081.7	914.9	1.300	M
4	异戊酸乙酯	108-64-5	C₇H₁₄O₂	130.2	1 105.5	971.4	1.248
5	3-蒈烯	13466-78-9	C₁₀H₁₆	136.2	1 009.0	761.5	1.720
6	2-正戊基呋喃	3777-69-3	C₉H₁₄O	138.2	1 022.3	787.6	1.252
7	γ-戊内酯	108-29-2	C₅H₈O₂	100.1	989.4	720.2	1.411	D
8	γ-戊内酯	108-29-2	C₅H₈O₂	100.1	988.1	717.1	1.138	M
9	甲基异丁甲醇	105-30-6	C₆H₁₄O	102.2	883.4	498.2	1.587
10	2-己醇	626-93-7	C₆H₁₄O	102.2	840.7	417.1	1.565
11	甲酸丁酯	592-84-7	C₅H₁₀O₂	102.1	735.7	267.1	1.518
12	2, 3-丁二酮	431-03-8	C₄H₆O₂	86.1	872.1	475.3	1.166
13	2-甲基吡嗪	109-08-0	C₅H₆N₂	94.1	894.7	521.2	1.394
14	顺-3-己烯基丁酯	16491-36-4	C₁₀H₁₈O₂	170.3	1 008.2	760.0	1.986
15	甲酸异戊酯	110-45-2	C₆H₁₂O₂	116.2	875.9	482.9	1.636
16	乙酸丁酯	123-86-4	C₆H₁₂O₂	116.2	830.8	400.3	1.613
17	丙酸异丁酯	540-42-1	C₇H₁₄O₂	130.2	831.7	401.8	1.711
18	2-庚酮	110-43-0	C₇H₁₄O	114.2	868.2	467.6	1.720
19	异戊醇	123-51-3	C₅H₁₂O	88.1	891.4	515.1	1.493
20	异丁醛	78-84-2	C₄H₈O	72.1	761.8	299.3	1.287
21	莰烯	79-92-5	C₁₀H₁₆	136.2	930.3	588.6	1.211	M
22	莰烯	79-92-5	C₁₀H₁₆	136.2	933.3	594.7	1.632	D
23	2-甲基丁醛	96-17-3	C₅H₁₀O	86.1	803.6	357.4	1.398
24	L （-） -乳酸乙酯	687-47-8	C₅H₁₀O₃	118.1	783.2	328.3	1.525
25	α-蒎烯	80-56-8	C₁₀H₁₆	136.2	978.0	692.7	1.668
26	异丁酸异丁酯	97-85-8	C₈H₁₆O₂	144.2	867.4	466.1	1.319
27	正戊醇	71-41-0	C₅H₁₂O	88.1	816.6	377.3	1.505
28	2, 3-丁二醇	513-85-9	C₄H₁₀O₂	90.1	684.8	215.1	1.353
29	异丙醇	67-63-0	C₃H₈O	60.1	649.9	192.1	1.224
30	丙酸	79-09-4	C₃H₆O₂	74.1	520.4	126.3	1.254

Tab.3

Tab.4

Fig.4

Fig.5

Fig.6

Fig.7

Fig.8

Fig.9

Fig.10

Fig.11

Tab.5

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类别	编号	名称	规格	产地	购买渠道	真假	备注
水剂	XZP1	特润修护肌活精华露	50 mL	美国	专柜	真	参照样品
	XZP2	特润修护肌活精华露	50 mL	日本	旗舰店	真
	XZP3	特润修护肌活精华露	30 mL	英国	旗舰店	真	赠品
	XZP4	特润修护肌活精华露	15 mL	美国	旗舰店	真	赠品
	XZP5	特润修护肌活精华露	7 mL	美国	旗舰店	真	赠品
	XZP6	特润修护肌活精华露	50 mL	英国	电商平台B	真
	XZP7	特润修护肌活精华露	50 mL	英国	电商平台C	假
	XZP8	特润修护肌活精华露	100 mL	英国	电商平台A	假
	XZP9	特润修护肌活精华露	100 mL	英国	电商平台C	假
	XZP10	特润修护肌活精华露	100 mL	英国	个人提供	假
乳剂	CTZXG-1	釉感焕彩多效妆前乳	40 g	中国	生产企业提供	真	企业生产
乳剂	CTZXG-2	釉感焕彩多效妆前乳	40 g	中国	生产企业提供	假	企业收集
膏霜	GBSS-1	高保湿霜	125 mL	美国	专柜	真	参照样品
	GBSS-2	高保湿霜	50 mL	日本	专柜	真
	GBSS-3	高保湿霜	125 mL	美国	旗舰店	真
	GBSS-4	高保湿霜	125 mL	美国	电商平台A	假
	GBSS-5	高保湿霜	125 mL	美国	电商平台B	真
	GBSS-6	高保湿霜	125 mL	美国	电商平台C	假
	GBSS-7	高保湿霜	125 mL	美国	电商平台C	假

编号	化合物	CAS号	分子式	分子量	保留指数	保留时间/sec	相对迁移时间/RIP ral.	备注
1	已腈	628-73-9	C₆H₁₁N	97.2	883.8	497.8	1.589
2	2-己烯醛	505-57-7	C₆H₁₀O	98.1	816.6	378.3	1.510
3	3-甲基戊酸	105-43-1	C₆H₁₂O₂	116.2	793.2	343.9	1.599
4	β-蒎烯	127-91-3	C₁₀H₁₆	136.2	1 010.0	758.6	1.722
5	苯乙醛	122-78-1	C₈H₈O	120.2	997.9	735.0	1.541
6	丙酸乙酯	105-37-3	C₅H₁₀O₂	102.1	696.9	226.1	1.457	D
7	异戊醛	590-86-3	C₅H₁₀O	86.1	687.7	217.5	1.408
8	丙硫醇	107-03-9	C₃H₈S	76.2	677.2	210.1	1.355
9	异丁醛	78-84-2	C₄H₈O	72.1	568.3	146.3	1.282
10	2-乙基-3, 5-二甲基吡嗪	13925-07-0	C₈H₁₂N₂	136.2	1 084.9	922.2	1.745
11	丁酸苄酯	103-37-7	C₁₁H₁₄O₂	178.2	1 357.1	1 874.4	1.938
12	己酸异戊酯	2198-61-0	C₁₁H₂₂O₂	186.3	1 312.1	1 667.0	2.131
13	苯甲酸乙酯	93-89-0	C₉H₁₀O₂	150.2	1 309.4	1 655.6	1.256
14	2-甲基丁醛	96-17-3	C₅H₁₀O	86.1	796.5	348.5	1.402
15	叔丁醇	75-65-0	C₄H₁₀O	74.1	687.1	217.1	1.138
16	丙酸正丙酯	106-36-5	C₆H₁₂O₂	116.2	779.9	325.2	1.209
17	丙酸异丁酯	540-42-1	C₇H₁₄O₂	130.2	819.4	382.6	1.713
18	异戊二烯	78-79-5	C₅H₈	68.1	550.5	137.9	1.211	M
19	异戊二烯	78-79-5	C₅H₈	68.1	550.5	137.9	1.451	D
20	DL-2-羟基-4-甲基戊酸乙酯	10348-47-7	C₈H₁₆O₃	160.2	787.7	336.1	1.894
21	3-戊酮	96-22-0	C₅H₁₀O	86.1	624.7	176.4	1.111	M
22	3-戊酮	96-22-0	C₅H₁₀O	86.1	622.2	174.9	1.371	D
23	丁酸乙酯	105-54-4	C₆H₁₂O₂	116.2	695.8	225.1	1.208

编号	相似度	编号	相似度	编号	相似度	编号	相似度
XZP1	1.000	XZP6	0.992	CTZQR1	1.000	GBSS4	0.067
XZP2	0.991	XZP7	0.488	CTZQR2	0.003	GBSS5	0.999
XZP3	0.968	XZP8	0.076	GBSS1	1.000	GBSS6	0.070
XZP4	0.993	XZP9	0.284	GBSS2	0.998	GBSS7	0.067
XZP5	0.992	XZP10	0.849	GBSS3	0.999

Authenticity identification of cosmetics based on headspace-gas chromatography-ion mobility spectrometry and headspace-gas chromatography-mass spectrometry technologies

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