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使用液相色谱-串联质谱联用技术同时分析化妆品中的单乙醇胺、二乙醇胺和三乙醇胺。

Simultaneous analysis of mono-, di-, and tri-ethanolamine in cosmetic products using liquid chromatography coupled tandem mass spectrometry.

作者信息

Shin Kyong-Oh, Lee Yong-Moon

机构信息

College of Pharmacy, Chungbuk National University, 1 Chungdae-Ro, Seowon-Ku, Chongju, 362-763, Korea.

出版信息

Arch Pharm Res. 2016 Jan;39(1):66-72. doi: 10.1007/s12272-015-0677-5. Epub 2015 Nov 14.

Abstract

Alkanolamines such as monoethanolamine (MEA), diethanolamine (DEA), and triethanolamine (TEA) are used as wetting agents in shampoos, lotions, creams, and other cosmetics. DEA is widely used to provide lather in shampoos and maintain a favorable consistency in lotions and creams. Although DEA is not harmful, it may react with other ingredients in the cosmetic formula after extended storage periods to form an extremely potent carcinogen called nitrosodiethanolamine (NDEA), which is readily absorbed through the skin and has been linked to the development of stomach, esophagus, liver, and bladder cancers. The purpose of this study was to develop a simultaneous quantification method for measurement of MEA, DEA, and TEA in cosmetic products. Liquid chromatography coupled tandem mass spectrometry (LC-MS/MS) was performed using a hydrophilic interaction liquid chromatography (HILIC) column with isocratic elution containing acetonitrile and 5 mM ammonium formate in water (88:12, v/v). Identification and quantification of alkanolamines were performed using MS/MS monitoring to assess the transition from precursor to product ion of MEA (m/z, 61.1 → 44.0), DEA (m/z, 106.1 → 88.0), TEA (m/z, 150.1 → 130.0), and the internal standard triethylamine (m/z, 102.2 → 58.0). Alkanolamines extractions were simplified using a single extraction with acetonitrile in the cosmetic matrix. Performance of the method was evaluated with quality parameters such as specificity, carry-over, linearity and calibration, correlation of determination (R(2)), detection limit, precision, accuracy, and recovery. Calibration curves of MEA (2.9-1000 ppb), DEA (1-1000 ppb), and TEA (1-1000 ppb) were constructed by plotting concentration versus peak-area ratio (analyte/internal standard with a correlation coefficient greater than 0.99). The intra- and inter-assay accuracy ranged from 92.92 to 101.15 % for all analytes. The intra- and inter-assay precision for MEA, DEA, and TEA showed all coefficients of variance were less than 9.38 % for QC samples. Limits of detection and limits of quantification were 2.00 and 15.63 ppb for MEA, 0.49 and 1.96 ppb for DEA, and 0.49 and 1.96 ppb for TEA, respectively. This novel quantification method simplified sample preparation and allowed accurate and reproducible quantification of alkanolamines in the ng/g cosmetic weight (ppb) range for several cosmetic products.

摘要

单乙醇胺(MEA)、二乙醇胺(DEA)和三乙醇胺(TEA)等链烷醇胺被用作洗发水、乳液、面霜及其他化妆品中的湿润剂。DEA被广泛用于使洗发水产生泡沫,并保持乳液和面霜良好的稠度。虽然DEA本身无害,但在化妆品配方中长时间储存后,它可能会与其他成分发生反应,形成一种极具致癌性的物质——亚硝基二乙醇胺(NDEA),这种物质很容易通过皮肤吸收,并与胃癌、食管癌、肝癌和膀胱癌的发生有关。本研究的目的是开发一种同时测定化妆品中MEA、DEA和TEA的定量方法。采用亲水相互作用液相色谱(HILIC)柱,以乙腈和5 mM甲酸铵水溶液(88:12,v/v)等度洗脱,进行液相色谱-串联质谱(LC-MS/MS)分析。通过MS/MS监测对链烷醇胺进行鉴定和定量,以评估MEA(m/z,61.1→44.0)、DEA(m/z,106.1→88.0)、TEA(m/z,150.1→130.0)以及内标三乙胺(m/z,102.2→58.0)从前体离子到产物离子的转变。在化妆品基质中,用乙腈单次萃取简化了链烷醇胺的萃取过程。该方法的性能通过特异性、残留、线性与校准、测定相关性(R(2))、检测限、精密度、准确度和回收率等质量参数进行评估。通过绘制浓度与峰面积比(分析物/内标,相关系数大于0.99)构建了MEA(2.9 - 1000 ppb)、DEA(1 - 1000 ppb)和TEA(1 - 1000 ppb)的校准曲线。所有分析物的批内和批间准确度范围为92.92%至101.15%。对于质量控制样品,MEA、DEA和TEA的批内和批间精密度显示所有变异系数均小于9.38%。MEA的检测限和定量限分别为2.00和15.63 ppb,DEA为0.49和1.96 ppb,TEA为0.49和1.96 ppb。这种新颖的定量方法简化了样品制备过程,并能够对几种化妆品中ng/g化妆品重量(ppb)范围内的链烷醇胺进行准确且可重复的定量。

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