超高效液相色谱法测定口腔护理产品中异噻唑啉酮类含量

doi:10.3969/j.issn.2097-2806.2023.09.016

摘要/Abstract

摘要：

采用超高效液相色谱法测定口腔护理产品中异噻唑啉酮类含量。通过HyperSep反相C8/苯磺酸离子交换器（HyperSep C8/BSAIE），Sep-Pak C18吸附剂的固相萃取（SPE）及超高效液相色谱/二极管阵列检测器（UPLC/DAD）用于同时测定口腔护理产品中甲基异噻唑啉酮（MI）和甲基氯异噻唑啉酮（MCI）。结果发现，HyperSep C8/BSAIE和UPLC/DAD的洗脱溶剂为混合物（乙腈和甲醇体积比2:1），较佳检测波长为255 nm；该方法具有良好的线性范围（0.005~10 µg/mL），测定系数（R²，0.997~0.999），检测限（LOD，0.001~0.002 µg/g）；在检测低（0.07 µg/mL）、中（3 µg/mL）和高（15 µg/mL）质量浓度的标准混合物时，相对标准偏差RSD<3%。共研究了12个口腔护理样品，MI含量为nd~0.89 µg/g，MCI含量为nd~0.62 µg/g。根据样品的类型，回收率在95.33%~101.43%之间。

关键词: 异噻唑啉酮, 对羟基苯甲酸酯, 化妆品, 固相萃取, 超高效液相色谱

Abstract:

The purpose of this paper is to determine the content of isothiazolinones in oral care products by ultra performance liquid chromatography. A HyperSep reversed-phase C8/BSAIE ion exchanger, solid phase extraction （SPE） with Sep-Pak C18 sorbent and an ultra performance liquid chromatography/diode array detector （UPLC/DAD） were used for the simultaneous determination of methylisothiazolinone （MI） and methylchloroisothiazolinone （MCI） in oral care products. The results find that the eluting solvents for HyperSep C8/BSAIE and UPLC/DAD are mixtures （acetonitrile/methanol, volume ratio 2:1） with an optimum detection wavelength of 255 nm. The method has a good linear range （0.005-10 µg/mL）, the coefficient of determination （R²） ranges from 0.997 to 0.999, and the limit of detection （LOD） is in the range of 0.001-0.002 µg/g. The relative standard deviation RSD is less than 3% for the detection of standard mixtures at low （0.07 µg/mL）, medium （3 µg/mL） and high （15 µg/mL） concentrations. A total of 12 oral care samples are studied, with the reaching concentrations of nd-0.89 µg/g for MI and nd-0.62 µg/g for MCI. Recoveries range from 95.33% to 101.43% depending on the type of sample.

Key words: isothiazolinone, parabens, cosmetics, solid phase extraction, ultra performance liquid chromatography

中图分类号:

TQ658

宋青梅, 杜丰. 超高效液相色谱法测定口腔护理产品中异噻唑啉酮类含量[J]. 日用化学工业（中英文）, 2023, 53(9): 1108-1114.

Song Qingmei, Du Feng. Determination of thiazolidinones in oral care products by ultra performance liquid chromatography[J]. China Surfactant Detergent & Cosmetics, 2023, 53(9): 1108-1114.

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种类	样品	MI含量/ （μg/g）	MCI含量/ （μg/g）
牙膏	A1	0.13±0.05	0.11±0.04
	A2	0.10±0.04	0.21±0.06
	A3	0.05±0.01	0.10±0.04
	A4	0.07±0.01	0.31±0.07
漱口水	B1	0.26±0.02	0.11±0.02
	B2	0.41±0.03	0.31±0.07
	B3	0.35±0.03	0.10±0.02
	B4	0.52±0.06	0.12±0.02
口气清新剂	C1	0.21±0.04	0.62±0.08
	C2	0.27±0.06	0.23±0.05
	C3	0.33±0.08	0.31±0.07
	C4	0.27±0.06	0.12±0.02

物质	线性范围/（μg/mL）	R²	LOD/（μg/g）	LOQ/（μg/g）
MI	0.005~10	0.997	0.002±0.001	0.007±0.002
MCI	0.005~10	0.999	0.001±0.001	0.004±0.001

物质	质量浓度添加量/（μg/mL）	日内			日间
物质	质量浓度添加量/（μg/mL）	质量浓度/（μg/mL）	回收率/%	RSD/%	质量浓度/（μg/mL）	回收率/%	RSD/%
MI	0.07	0.07±0.002	101.14	2.40	0.07±0.004	99.28	5.32
	3	3.01±0.003	100.17	0.11	2.95±0.078	98.37	2.67
	15	14.30±0.035	95.33	0.24	14.30±0.035	95.33	0.24
MCI	0.07	0.07±0.001	101.43	1.41	0.07±0.002	100.00	2.86
	3	3.01±0.003	100.23	0.10	3.01±0.007	100.17	0.23
	15	14.53±0.013	96.87	0.09	14.53±0.007	96.67	0.05

样品类型	分析结果	萃取方法	测定方法	分析时间/min	线性范围/（μg/mL）	R²	LOD/ （ng/mL）	精度（RSD/%）	回收率/%	文献
化妆品	MI，MCI	溶剂萃取	UPLC-MS/MS	2.81	0.1~500 （MI）， 0.1~100 0 （MCI）	0.999 7 （MI）， 0.999 6 （MCI）	43	<7	99~111 （MI）， 93~104 （MCI）	[7]
化妆品、清洗剂和药品	MI，MCI，BA，SB，MP	超声波萃取	FLC/UV	27	330~13 330 （MI）， 250~10 000 （MCI）， 5 000~100 000 （BA）， 1 000~10 000 （SB）， 250~10 000 （MP）	0.999 6~0.999 9	60~4 380	0.39~3.45	69~119	[15]
化妆品和个人护理产品	MP，EP，PP，BP	织物相吸收性萃取	HPLC/UV	25.27	50~500	0.995 5	0.3~0.6	<5	88~122	[22]
食品、化妆品和药品	MP，EP，PP，BP	VA-DLLME- SFO，SA-CPE	CLC/UV	15	100~10 000	0.998	10~30 （VA-DLLME-SFO），30（SA-CPE）	<5	—	[11]
唾液和牙膏	MP，EP，PP，BP，nBP，iBP	SPE	HPLC/ UV-Vis	15	300~50 000	0.998 8~0.999 8	100~300	1~6.8	88~113	[23]
化妆品	MI，MCI	SPE	UPLC/DAD	24.7	8~20 000	0.997~0.999	1~2	3~6	95.33~101.43	本研究