Development of ultrasonic-assisted closed in-syringe extraction and derivatization for the determination of labile abietic acid and dehydroabietic acid in cosmetics.

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.