Liu Jianjun, Liu Mengge, Li Xiu, Lu Xiaomin, Chen Guang, Sun Zhiwei, Li Guoliang, Zhao Xianen, Zhang Shijuan, Song Cuihua, Wang Hua, Suo Yourui, You Jinmao
The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu 273165, Shandong, China; Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, Qufu Normal University, Qufu 273165, Shandong, China.
The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu 273165, Shandong, China; Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, Qufu Normal University, Qufu 273165, Shandong, China; Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining 810001, China.
J Chromatogr A. 2014 Dec 5;1371:20-9. doi: 10.1016/j.chroma.2014.10.059. Epub 2014 Oct 30.
Two resin acids, abietic acid (AA) and dehydroabietic acid (DHAA), in cosmetics may cause allergy or toxicoderma, but remain inaccurately investigated due to their lability. In this work, an accurate, sensitive, efficient and convenient method, utilizing the ultrasonic-assisted closed in-syringe extraction and derivatization (UCSED) prior to high performance liquid chromatography (HPLC) coupled with fluorescence detection (FLD) and on-line tandem mass spectra (MS/MS), has been developed. Analytes are extracted by acetonitrile (10/1, v/m) in a sealed syringe under safe condition (60°C; 15 min; nitrogen atmosphere) and then in-syringe derivatized by 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-d]imidazol-1-yl) ethyl-p-toluenesulfonate (ANITS) (8-fold, 93°C, 30 min, DMF as co-solvent, K2CO3 as catalyst). In UCSED, derivatization contributes to increase both analytical sensitivity and stability of analytes. Excellent linearity (r2≥0.9991) is achieved in wide range (75-3000 ng/mL (AA); 150-4500 ng/mL (DHAA)). Quite low detection limits (AA: 8.2-10.8 ng/mL; DHAA: 19.4-24.3 ng/mL) and limits of analyte concentration (LOAC) (AA: 30.0-44.5 ng/mL; DHAA: 70.9-86.7 ng/mL) ensure the trace analysis. This method is applied to the analysis of cosmetic samples, including depilatory wax strip, liquid foundation, mascara, eyeliner, eyebrow pencil and lip balm. No additional purification is required and no matrix effect is observed, demonstrating obvious advantages over conventional pretreatment such as solid phase extraction (SPE). Accuracy (RE: -3.2% to 2.51%), precision (RSD: 1.29-2.84%), recovery (95.20-103.63%; 95.51-104.22%) and repeatability (<0.23%; <2.87%) are significantly improved. Furthermore, this work plays a guiding role in developing a reasonable method for labile analytes.
化妆品中的两种树脂酸，即枞酸（AA）和去氢枞酸（DHAA），可能会引起过敏或中毒性皮肤病，但由于它们的不稳定性，相关研究仍不准确。在本研究中，我们开发了一种准确、灵敏、高效且便捷的方法，该方法在高效液相色谱（HPLC）结合荧光检测（FLD）和在线串联质谱（MS/MS）之前，采用超声辅助封闭注射器萃取和衍生化（UCSED）。分析物在安全条件下（60°C；15分钟；氮气氛围）于密封注射器中用乙腈（10/1，v/m）萃取，然后在注射器中用2-(2-(蒽-10-基)-1H-萘并[2,3-d]咪唑-1-基)乙基对甲苯磺酸盐（ANITS）进行衍生化（8倍，93°C，30分钟，以N,N-二甲基甲酰胺作为共溶剂，碳酸钾作为催化剂）。在UCSED中，衍生化有助于提高分析物的灵敏度和稳定性。在较宽范围内（75 - 3000 ng/mL（AA）；150 - 4500 ng/mL（DHAA））实现了出色的线性（r2≥0.9991）。极低的检测限（AA：8.2 - 10.8 ng/mL；DHAA：19.4 - 24.3 ng/mL）和分析物浓度限值（LOAC）（AA：30.0 - 44.5 ng/mL；DHAA：70.9 - 86.7 ng/mL）确保了痕量分析。该方法应用于化妆品样品的分析，包括脱毛蜡纸、粉底液、睫毛膏、眼线笔、眉笔和唇膏。无需额外纯化，也未观察到基质效应，与固相萃取（SPE）等传统预处理方法相比具有明显优势。准确度（RE：-3.2%至2.51%）、精密度（RSD：1.29 - 2.84%）、回收率（95.20 - 103.63%；95.51 - 104.22%）和重复性（<0.23%；<2.87%）均有显著提高。此外，这项工作对开发针对不稳定分析物的合理方法具有指导作用。
