高效液相色谱法测定原料及化妆品中7种视黄醇及其衍生物的含量

doi:10.3969/j.issn.1001-1803.2022.08.012

摘要/Abstract

摘要：

建立了能够同时测定原料及化妆品中视黄醇及视黄醇6种衍生物（视黄醛、视黄醇乙酸酯、视黄醇丙酸酯、视黄醇棕榈酸酯、羟基频哪酮视黄酸酯和视黄醇视黄酸酯）的高效液相色谱的分析方法。样品用乙腈萃取,经ZORBAX Eclipse Plus C-18（250 mm×4.6 mm,5 μm）色谱柱分离,以乙腈和四氢呋喃为流动相,梯度洗脱,柱温30 ℃,流速1 mL/min,用二极管阵列检测器在多波长下同时测定原料及化妆品中7种视黄醇及其衍生物。结果显示,该方法的线性系数范围为0.999 7~1,回收率范围为92.37%~112.06%,精密度（RSD）范围为0.20%~6.14%。14批次样品的测定结果表明该方法有较高的可实用性和重现性,能很好地满足原料及化妆品的分析需求。

关键词: 视黄醇, 羟基频哪酮视黄酸酯, 视黄醇视黄酸酯, 高效液相色谱法

Abstract:

An analytical method for the determination of retinol and its six derivatives （retinal, retinyl acetate, retinyl propionate, retinyl palmitate, hydroxypinacolone retinoate and retinyl retinoate） in raw materials and cosmetics has been developed. The sample was extracted with acetonitrile, followed by high performance liquid chromatography （HPLC） determination with diode array detector （DAD）, then it was separated by ZORBAX Eclipse Plus C-18（250 mm×4.6 mm, 5 μm）using acetonitrile and tetrahydrofuran as the mobile phase with gradient elution. The column temperature was 30 ℃, and the flow rate was 1 mL/min. The diode array detector was used to detect seven kinds of retinols and their derivatives in raw materials and cosmetics at multi-wavelength. The method is successfully validated which shows a good linearity（0.999 7-1）with the limits of detection in the range of 0.5-2 μg/mL and quantification ranged from 1.5 to 6 μg/mL, respectively. Finally, the proposed analytical method is applied to the determination of retinol and its six derivatives in different dosage forms of cosmetic samples containing essence, emulsion and cream, with good relative recovery values （92.37%-112.06%）, and the precision （RSD） ranged from 0.20% to 6.14%. Thus, the results show that matrix effects are negligible. The method shows a good practicability and reproducibility through detection of 14 batches of samples. The good analytical features of the proposed method besides its simplicity and affordability, make it useful to carry out the quality control of cosmetic products. The establishment of this method is helpful for cosmetic enterprises to search for high-quality raw materials, controll the best balance between efficacy and measurement, verify whether the production process is reliable and ensure the stability of raw materials and product efficacy. At the same time, it provids reliable quality inspection means for enterprises when developing and producing products. This method not only meets the simultaneous determination of multiple components in batch samples, but also improves the detection efficiency and reduces the experimental cost. The establishment of this test method is of great significance for the market supervision of cosmetics and cosmetic raw materials.

Key words: retinol, hydroxypinacone retinoate（hpr）, retinyl retinoate, high performance liquid chromatography

中图分类号:

TQ658

闫秀芳,严晓娟,陈燕. 高效液相色谱法测定原料及化妆品中7种视黄醇及其衍生物的含量[J]. 日用化学工业, 2022, 52(8): 868-874.

Yan Xiufang,Yan Xiaojuan,Chen Yan. Determination of 7 retinol and its derivatives in raw materials and cosmetics by high performance liquid chromatography[J]. China Surfactant Detergent & Cosmetics, 2022, 52(8): 868-874.

图/表 8

表 1

表 2

图 1

图 2

表 3

图 3

表 4

加标回收率和精密度"

化合物	添加水平/（μg/mL）	测定值/（μg/mL）与回收率/%				RSD/%
化合物	添加水平/（μg/mL）		膏霜	乳液	精华液	RSD/%
视黄醇	5	测定值	5.04~5.20	4.88~5.39	4.66~5.04	3.99
	5	回收率	100.83~104.01	97.58~107.87	93.28~100.71	3.99
	10	测定值	9.97~10.18	10.21~10.29	10.03~10.27	1.22
	10	回收率	99.72~101.80	102.05~102.90	100.30~102.71	1.22
	20	测定值	20.50~21.10	19.05~21.14	20.37~20.57	3.02
	20	回收率	102.50~105.4	95.23~105.72	101.83~102.84	3.02
视黄醛	10	测定值	9.72~10.07	9.54~10.40	9.67~10.49	3.26
	10	回收率	97.23~100.68	95.37~104.00	96.70~104.93	3.26
	20	测定值	19.36~20.20	19.68~19.99	19.56~20.11	1.34
	20	回收率	96.82~101.00	98.41~99.94	97.81~100.54	1.34
	40	测定值	40.28~40.36	39.91~40.32	39.84~40.49	0.53
	40	回收率	100.69~100.89	99.77~100.79	99.60~101.23	0.53
视黄醇乙酸酯	10	测定值	9.88~10.59	9.88~10.98	10.32~10.37	3.32
	10	回收率	98.76~105.94	98.76~109.80	103.18~103.73	3.32
	20	测定值	19.31~20.91	20.42~21.69	18.93~20.42	4.05
	20	回收率	96.57~104.57	102.09~108.44	94.64~102.09	4.05
	40	测定值	39.29~41.72	38.80~41.39	38.58~40.62	2.72
	40	回收率	98.24~104.31	96.99~103.48	96.44~101.55	2.72
视黄醇丙酸酯	5	测定值	5.16~5.32	5.11~5.13	5.04~5.12	1.48
	5	回收率	103.21~106.50	102.28~102.64	100.87~102.38	1.48
	10	测定值	10.23~10.56	10.26~10.30	10.28~10.29	0.94
	10	回收率	102.34~105.56	102.65~102.95	102.79~102.86	0.94
	20	测定值	20.28~20.41	20.34~20.37	20.31~20.34	0.20
	20	回收率	101.39~102.06	101.71~101.85	101.57~101.71	0.20
视黄醇视黄酸酯	10	测定值	9.40~10.48	9.24~10.10	9.93~10.66	4.71
	10	回收率	93.95~104.81	92.37~100.96	99.35~106.57	4.71
	20	测定值	19.18~19.66	18.64~20.10	19.13~19.61	2.16
	20	回收率	95.88~98.30	93.22~100.52	95.67~98.07	2.16
	40	测定值	37.29~42.02	38.07~38.65	37.57~38.03	3.58
	40	回收率	93.24~105.05	95.17~96.63	93.91~95.08	3.58
视黄醇棕榈酸酯	10	测定值	9.45~11.21	9.40~9.43	9.37~10.06	6.14
	10	回收率	94.55~112.06	94.03~94.26	93.71~100.57	6.14
	20	测定值	19.27~20.44	18.73~19.54	20.24~20.50	3.10
	20	回收率	96.36~102.20	93.63~97.69	101.20~102.52	3.10
	40	测定值	38.25~41.18	38.78~40.48	40.51~42.85	3.47
	40	回收率	95.61~102.95	96.96~101.20	101.26~107.12	3.47
羟基频哪酮视黄酸酯	10	测定值	9.57~10.03	9.71~10.24	9.67~9.86	2.15
	10	回收率	95.70~100.29	97.13~102.44	96.70~98.57	2.15
	20	测定值	19.76~20.46	19.10~20.37	20.23~20.50	2.20
	20	回收率	98.78~102.30	95.48~101.87	101.15~102.51	2.20
	40	测定值	39.02~40.36	39.17~40.11	40.77~41.92	2.11
	40	回收率	97.56~100.89	97.92~100.29	101.94~104.81	2.11

表 4

表 5

参考文献 13

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化合物	线性方程	相关系数	线性范围/（μg/mL）	检出限/（μg/mL）	定量限/（μg/mL）
视黄醇	y=29.561x-14.029	0.999 7	5~80	1.0	3.0
视黄醛	y=75.307x-38.208	1	10~160	1.0	3.0
视黄醇乙酸酯	y=18.118x-10.934	0.999 8	10~160	1.0	3.0
视黄醇丙酸酯	y=71.561x-26.664	0.999 8	5~80	0.5	1.5
视黄醇视黄酸酯	y=25.807x-4.4583	0.999 7	10~160	2.0	6.0
视黄醇棕榈酸酯	y=37.167x-72.483	0.999 9	10~160	2.0	6.0
羟基频哪酮视黄酸酯	y=69.71x-32.001	0.999 9	10~160	1.0	3.0

样品类型	样品序号	测试结果（w/%）
样品类型	样品序号	视黄醇	视黄醛	视黄醇乙酸酯	视黄醇丙酸酯	视黄醇视黄酸酯	视黄醇棕榈酸酯	羟基频哪酮视黄酸酯
精华液	样品1	0.30					0.40
	样品2	0.08
	样品3		0.000 4
膏霜	样品4						0.15
	样品5							0.20
	样品6					0.12
乳液	样品7			0.12
乳液	样品8				0.08
常规原料	原料1	2.99					5.02
	原料2						98.45
	原料3	47.54
	原料4							6.62
	原料5							5.69
脂质体包裹原料	原料6		0.000 8

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