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

Abstract

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

CLC Number:

TQ658

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.

Figures/Tables 5

Tab. 1

Fig. 1

Tab. 2

Tab. 3

Tab. 4

References 23

[1]	Wu R R, Li G R, Long M, et al. The need for testing methylisothiazolinones as preservatives in food detergents[J]. China Detergent Industry, 2021, 2: 91-94.
[2]	Yang Y C, Yan J, Zhao H L B. Determination of three isothiazolinone preservatives in children’s cosmetics by liquid chromatography-tandem mass spectrometry[J]. Journal of Analytical Sciences, 2019, 35 (1) : 80-84.
[3]	Chen C, Cui C Z, Gao Y L, et al. Analysis of the use of isothiazolinones as preservatives in drench cosmetics[J]. Journal of Japanese Chemical Science, 2022, 45 (3) : 26-31, 57.
[4]	Aalto-Korte K, Koskela K, Pesonen M. 12-year data on dermatologic cases in the Finnish Register of Occupational Diseases I: Distribution of different diagnoses and main causes of allergic contact dermatitis[J]. Contact Dermatitis, 2020, 82 (6) : 337-342. doi: 10.1111/cod.13488 pmid: 32037572
[5]	Abad-Gil L, Lucas-Sanchez S, Gismera M J, et al. Determination of paraben-, isothiazolinone- and alcohol-type preservatives in personal care products by HPLC with dual (diode-array and fluorescence) detection[J]. Microchem. J., 2021, 160: 105613. doi: 10.1016/j.microc.2020.105613
[6]	Alvarez-Rivera G, Dagnac T, Lores M, et al. Determination of isothiazolinone preservatives in cosmetics and household products by matrix solid-phase dispersion followed by high-performance liquid chromatography-tandem mass spectrometry[J]. J. Chromatogr. A., 2012, 1270: 41-50. doi: 10.1016/j.chroma.2012.10.063 pmid: 23182288
[7]	Wittenberg J B, Canas B J, Zhou W, et al. Determination of methylisothiazolinone and methylchloroisothiazolinone in cosmetic products by ultra high performance liquid chromatography with tandem mass spectrometry[J]. J. Sep. Sci., 2015, 38: 2983-2988. doi: 10.1002/jssc.201500365 pmid: 26103935
[8]	Schettgen T, Bertram J, Kraus T. Quantification of N-methylmalonamic acid in urine as metabolite of the biocides methylisothiazolinone and chloromethylisothiazolinone using gas chromatography-tandem mass spectrometry[J]. J. Chromatogr. B., 2017, 1044: 185-193.
[9]	Le Hoa T H, Hung V T N, do Trang T, et al. Development and validation of an HPLC method for simultaneous assay of MCI and MI in shampoos containing plant extracts[J]. Int. J. Anal. Chem., 2019 (6) : 1-10.
[10]	Chilbule A, Singh R, Mann B, et al. Development and validation of an analytical method for determination of bronopol and kathon preservative in milk[J]. J. Food Sci. Technol., 2019, 56: 3170-3176. doi: 10.1007/s13197-019-03807-5 pmid: 31205373
[11]	Chen Z F, Ying G G, Lai H J, et al. Determination of biocides in different environmental matrices by use of ultra-high-performance liquid chromatography-tandem mass spectrometry[J]. Anal. Bioanal. Chem., 2012, 404: 3175-3188. doi: 10.1007/s00216-012-6444-2
[12]	Heo J J, Kim U J, Oh J E, et al. Simultaneous quantitative analysis of four isothiazolinones and 3-iodo-2-propynyl butyl carbamate in hygienic consumer products[J]. Environ. Eng. Res., 2018, 24: 137-143. doi: 10.4491/eer.2018.144
[13]	Goodier M C, Siegel P D, Zang L Y, et al. Isothiazolinone in residential interior wall paint: A high-performance liquid chromatographic-mass spectrometry analysis[J]. Dermat., 2018, 29: 332-338.
[14]	Rosero-Moreano M, Canellas E, Nerín C. Three-phase hollow-fiber liquid-phase microextraction combined with HPLC-UV for the determination of isothiazolinone biocides in adhesives used for food packaging materials[J]. J. Sep. Sci., 2014, 37: 272-280. doi: 10.1002/jssc.201300840 pmid: 24302646
[15]	Baranowska I, Wojciechowska I, Solarz N, et al. Determination of preservatives in cosmetics, cleaning agents and pharmaceuticals using fast liquid chromatography[J]. J. Chromatogr. Sci., 2014, 52: 88-94. doi: 10.1093/chromsci/bms210 pmid: 23324734
[16]	Chen X X, Tan X L, Du G X, et al. Determination of methylchloroisothiazolinone and methylisothiazolinone in cosmetic products[J]. Guangdong Chemical Industry, 2020, 47 (3) : 191-193.
[17]	Goodier M C, Siegel P D, Zang L Y, et al. Isothiazolinone in residential interior wall paint: a high-performance liquid chromatographic-mass spectrometry analysis[J]. Dermatitis, 2018, 29 (6) : 332-338. doi: 10.1097/DER.0000000000000410 pmid: 30346324
[18]	Goodier M C, Zang L Y, Siegel P D, et al. Isothiazolinone content of US consumer adhesives: ultrahigh-performance liquid chromatographic mass spectrometry analysis[J]. Dermatitis, 2019, 30 (2) : 129-134. doi: 10.1097/DER.0000000000000455 pmid: 30829801
[19]	Lin Q B, Wang T J, Song H, et al. Analysis of isothiazolinone biocides in paper for food packaging by ultra-high-performance liquid chromatography—tandem mass spectrometry[J]. Food Addit. Contam. Part. A, 2010, 27: 1775-1781. doi: 10.1080/19440049.2010.521896
[20]	Fei T, Li H, Ding M, et al. Determination of parabens in cosmetic products by solid-phase microextraction of poly(ethylene glycol) diacrylate thin film on fibers and ultra high-speed liquid chromatography with diode array detector[J]. J. Sep. Sci., 2011, 34: 1599-1606. doi: 10.1002/jssc.201100225 pmid: 21608130
[21]	Jardim V C, Melo L, Domingues D S, et al. Determination of parabens in urine samples by microextraction usingpacked sorbent and ultra-performance liquid chromatography coupled to tandem mass spectrometry[J]. J. Chromatogr. B., 2015, 974: 35-41. doi: 10.1016/j.jchromb.2014.10.026
[22]	Kaur R, Kaur R, Grover A, et al. Trace determination of parabens in cosmetics and personal care products using fabric-phase sorptive extraction and high-performance liquid chromatography with UV detection[J]. J. Sep. Sci., 2020, 43: 2626-2635. doi: 10.1002/jssc.201900978 pmid: 32259348
[23]	Zotou A, Sakla I, Tzanavaras P D. LC-determination of five paraben preservatives in saliva and toothpaste samples using UV detection and a short monolithic column[J]. J. Pharm. Biomed. Anal., 2010, 53: 785-789. doi: 10.1016/j.jpba.2010.05.018 pmid: 20541882

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

Determination of thiazolidinones in oral care products by ultra performance liquid chromatography

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