液相色谱-串联质谱法同时测定化妆品中19种氨基酸

doi:10.3969/j.issn.1001-1803.2019.10.010

Abstract

Abstract:

A method for the determination of 19 amino acids in cosmetics by liquid chromatography-tandem mass spectrometry with pre-column derivation was established. The samples were mixed with activated carbon and a small amount of water, heated, sonicated, centrifuged and then made up to a fixed volume with water. Then separated by Sharpsil-H C₁₈（2.1 mm×100 mm×3 μm）column. The acetonitrile- ammonium acetate system was used as mobile phase, with gradient elution, electrospray positive ion-multiple reaction mode detection. The results show that the linear relationship is good with the concentration of amino acid in the range of 0.005-100 mg/L. The correlation coefficient was 0.991 7-0.999 9.The detection limits of 19 amino acids ranged from 1 to 15 μg/L, and the recovery rates of cosmetic samples were 83.4%-93.6%.

Key words: cosmetics, amino acid, liquid chromatography-tandem mass spectrometry, pre-column derivation, phthalaldehyde

CLC Number:

TQ658

ZHOU Jin-bo,ZHU Zhi-jia. Simultaneous determination of 19 amino acids in cosmetics byliquid chromatography-tandem mass spectrometry[J].China Surfactant Detergent & Cosmetics, 2019, 49(10): 688-693.

Figures/Tables 5

Fig. 1

Tab. 1

Tab. 2

Tab. 3

Tab. 4

References 14

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氨基酸衍生物	前驱离子（m/z）	子离子（m/z）	毛细管电压/V	碰撞能量/V	氨基酸衍生物	前驱离子（m/z）	子离子（m/z）	毛细管电压/V	碰撞能量/V
丙氨酸（Ala）	292	189^* 144	60	20 30	蛋氨酸（Met）	354	175^* 130	50	20 40
谷氨酸（Glu）	352	247^* 175	50	20 30	天冬氨酸（Asp）	338	233^* /	50	20 20
亮氨酸（Leu）	336	175^* 130	40	25 30	组氨酸（His）	360	315^* 210	30	10 20
丝氨酸（Ser）	310	205^* 117	50	20 30	苯丙氨酸（Phe）	370	265^* 220	60	20 20
精氨酸（Arg）	379	229^* 335	40	10 15	酪氨酸（Tyr）	386	281^* 222	60	20 20
谷氨酰胺（Gln）	351	130^* 222	40	20 20	色氨酸（Trp）	409	188^* 205	30	10 20
赖氨酸（Lys）	351	284^* /	60	15 15	半胱氨酸（Cys）	354	135^* 220	60	20 20
苏氨酸（Thr）	324	219^* 175	50	20 25	异亮氨酸（Ile）	336	186^* 231	60	20 15
天冬酰胺（Asn）	337	188^* 232	40	20 20	缬氨酸（Val）	322	217^* 172	60	20 20
甘氨酸（Gly）	280	175^* 162	50	20 25

氨基酸	保留时间/min	线性范围/（mg·L^-1）	回归方程	相关系数	检出限/（μg·L^-1）
丝氨酸（Ser）	7.031	0.050~100	A=8.2×10³ρ-1.3×10³	0.996 9	15
赖氨酸（Lys）	9.011	0.010~100	A=1.9×10⁴ρ+4.4×10⁴	0.991 9	3
甘氨酸（Gly）	9.783	0.005~100	A=7.4×10⁴ρ+3.8×10⁵	0.993 9	1
组氨酸（His）	10.662	0.005~100	A =1.1×10⁵ρ+4.1×10⁵	0.991 9	1
苏氨酸（Thr）	11.501	0.005~100	A =1.7×10⁵ρ+1.4×10⁵	0.990 7	1
精氨酸（Arg）	12.167	0.005~100	A =2.0×10⁵ρ+1.6×10⁵	0.999 0	1
谷氨酰胺（Gln）	13.006	0.005~100	A =4.0×10⁶ρ-4.0×10⁵	0.998 0	1
半胱氨酸（Cys）	13.833	0.005~100	A =4.2×10⁶ρ-4.5×10⁵	0.999 4	1
丙氨酸（Ala）	14.168	0.005~100	A =4.0×10⁴ρ-8.4×10⁴	0.910 0	1
酪氨酸（Tyr）	14.663	0.010~100	A =1.1×10⁶ρ-3.2×10⁵	0.990 6	3
谷氨酸（Glu）	17.881	0.010~100	A =1.0×10⁶ρ-1.0×10⁵	0.998 5	3
缬氨酸（Val）	18.831	0.010~100	A =7.7×10⁴ρ-5.7×10³	0.991 8	3
蛋氨酸（Met）	19.804	0.005~100	A =7.7×10⁴ρ-1.9×10³	0.999 9	1
苯丙氨酸（Phe）	20.689	0.050~100	A =1.6×10⁵ρ-5.3×10⁴	0.999 1	15
色氨酸（Trp）	21.167	0.005~100	A =1.5×10⁵ρ+3.0×10⁴	0.999 3	1
亮氨酸（Leu）	21.882	0.005~100	A =1.7×10⁵ρ+1.6×10⁵	0.991 7	1
异亮氨酸（Ile）	22.546	0.005~100	A =1.6×10⁵ρ-8.3×10⁴	0.998 3	1
天冬酰胺（Asn）	23.451	0.010~100	A =1.6×10⁴ρ-4.0×10³	0.999 3	3
天冬氨酸（Asp）	25.357	0.005~100	A =7.8×10³ρ-2.6×10⁴	0.999 6	1

氨基酸	初始值/μg	加入值/μg	测得值/μg	回收率/%	平均回收率/%	RSD/%
丝氨酸（Ser）	1 053.4	5	1 058.1	94.0	89.7	1.32
		10	1 061.3	79.0
		100	1 149.6	96.2
苏氨酸（Thr）	101.3	5	106.3	100.0	87.7	2.56
		10	108.2	69.0
		100	195.5	94.2
丙氨酸（Ala）	550.2	5	554.3	82.0	93.6	1.86
		10	560.2	100.0
		100	648.9	98.7
精氨酸（Arg）	901.6	5	904.3	54.0	86.1	1.31
		10	912.2	106.0
		100	999.8	98.2
甘氨酸（Gly）	802.3	5	806.2	78.0	90.3	1.45
		10	811.3	90.0
		100	905.2	102.9
赖氨酸（Lys）	51.5	5	55.7	84.0	83.4	3.31
		10	58.1	66.0
		100	151.6	100.1
组氨酸（His）	52.3	5	57.1	96.0	87.3	3.27
		10	58.1	58.0
		100	160.1	107.8
亮氨酸（Leu）	150.4	5	153.5	62.0	85.6	2.61
		10	159.6	92.0
		100	253.1	102.7
天冬氨酸（Asp）	151.2	5	153.8	52.0	86.4	2.73
		10	162.4	112.0
		100	246.3	95.1

序号	氨基酸	面霜中氨基酸含量/（g/100 g）		保湿凝乳中氨基酸含量/（g/100 g）		爽肤水中氨基酸含量/（g/100 g）
序号	氨基酸	本法均值	AAA法均值	本法均值	AAA法均值	本法均值	AAA法均值
1	丝氨酸（Ser）	0.035	0.033	0.031	0.034	0.026	0.024
2	苏氨酸（Thr）	0.008	0.009	0.003	0.003	0.002	0.003
3	丙氨酸（Ala）	0.018	0.019	0.017	0.018	0.011	0.013
4	精氨酸（Arg）	0.021	0.023	0.019	0.017	0.015	0.013
5	甘氨酸（Gly）	0.029	0.024	0.028	0.029	0.016	0.015
6	赖氨酸（Lys）	0.003	0.003	0.004	0.005	0.003	0.004
7	谷氨酸（Glu）	0.003	0.002	0.004	0.004
8	组氨酸（His）	0.001	0.001	0.004	0.003	0.001	0.002
9	酪氨酸（Tyr）	0.003	0.004	0.003	0.002
10	亮氨酸（Leu）	0.001	0.001	0.001	0.001	0.001	0.001
11	异亮氨酸（Ile）	0.001	0.002	0.001	0.001
12	缬氨酸（Val）	0.004	0.003	0.004	0.003
13	苯丙氨酸（Phe）	0.003	0.004	0.001	0.001
14	天冬氨酸（Asp）	0.009	0.009	0.004	0.006	0.003	0.002
15	合计	0.139	0.137	0.124	0.127	0.078	0.077

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Simultaneous determination of 19 amino acids in cosmetics byliquid chromatography-tandem mass spectrometry

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