A study on the applicability of one-step vortex extraction and purification combined with gas chromatography-tandem mass spectrometry for analysis of four skin penetration enhancers in cosmetics.

Based on one-step vortex extraction and purification combined with gas chromatography-tandem mass spectrometry (GC-MS/MS), we established a simple, rapid, and efficient method for the simultaneous determination of four skin penetration enhancers in cosmetics, including isosorbide dimethyl ether, isopropyl myristate, N-butylsaccharin and Azone. The extraction procedure was performed in a centrifuge tube, allowing extraction and purification in a single step. The cosmetic sample was extracted by n-hexane-ethyl acetate (1:1, V/V), purified by silica gel and anhydrous magnesium sulfate as the solid phase purification agent, separated on a TG-5 ms column (30.0 m × 0.25 mm × 0.25 µ m), confirmed and detected by GC-MS/MS in the selected reaction monitoring (SRM) mode, and quantified by the internal standard method with Di-n­butyl phthalate-D4(DBP-D4) as the internal standard. The selections of a column, extraction solvent, and solid phase purification agent were optimized. Under the optimized conditions, the four skin penetration enhancers showed good linearities in the range of 0.02∼0.50 mg L - 1. The correlation coefficients (r) were 0.992 ∼ 0.997, exceeding the specifications requirements (r ≥ 0.990); The detection (LODs, S/N = 3) and quantification limits (LOQs, S/N = 10) of the method were 0.08 ∼ 0.12 mg kg-1 and 0.25 ∼ 0.40 mg kg-1, respectively. According to the cosmetic matrix in different formulation systems, the spiked recovery tests were carried out at three levels, i.e., low, medium, and high. The average recoveries of the analytes were 85.3% ∼ 95.6%, and the relative standard deviations (RSDs, n = 6) were 2.1% ∼ 7.8%. The established method was also employed to analyze cosmetics in the market. Azone, isosorbide dimethyl ether, and isopropyl myristate resulted as the most widely used skin penetration enhancers in cosmetics. The method established in this study has the advantages of operational simplicity, high sensitivity, good reproducibility, and low consumption of samples and solvents. Moreover, it can be used to determine skin penetration enhancers in cosmetics.

[Simultaneous determination of seven dimethylcyclosiloxanes in cosmetics of different formulation systems by gel permeation chromatography purification-gas chromatography-tandem mass spectrometry].

At present, the addition of dimethylcyclosiloxanes (DMCs) in cosmetics is being debated and no substantial progress has been made in their safety risk assessment because of the lack of a suitable analytical method. Therefore, it is of theoretical and practical significance to establish a method suitable for the determination of DMCs in cosmetics with different formulation systems. Accordingly, a method based on gel permeation chromatography (GPC) purification combined with gas chromatography-tandem mass spectrometry (GC-MS/MS) was developed for the determination of seven DMCs in cosmetics. The cosmetic samples were extracted by ethyl acetate-cyclohexane (1∶1, v/v), purified by gel permeation chromatography, separated on a DB-5ms column (30.0 m×0.25 mm×0.25 µm), confirmed and detected by gas chromatography-tandem mass spectrometry in the selected reaction monitoring (SRM) mode, and quantified by the internal standard method with n-hexadecane as the internal standard. Experiments were carried out using n-tetradecane, n-hexadecane, and n-octadecane as the internal standards, and based on the retention time in GPC and GC, n-hexadecane was found to be the suitable choice for further analyses. The extraction efficiency for the target compounds was tested in different solvents such as methanol, n-hexane, acetonitrile, ethyl acetate, and ethyl acetate-cyclohexane (1∶1, v/v). Given the high recovery, ethyl acetate-cyclohexane (1∶1, v/v) was selected as the extraction solvent for analyses. Among the three purification methods (analysis without purification, solid-phase extraction (SPE), and GPC purification), GPC was selected as the best method because of the minimal matrix interference to the target compounds. Under the optimized conditions, the seven DMCs showed good linearities in the range of 0.05-1.0 mg/L. The correlation coefficients (r) were 0.994-0.998, which were greater than the required of the specification (r≥0.990). The limits of detection (LODs, S/N=3) were 0.04-0.08 mg/kg, and the limits of quantification (LOQs, S/N=3) were 0.12-0.24 mg/kg. According to the cosmetic matrix in different formulation systems, standard addition recovery tests at three levels of low, medium, and high were carried out. The average recovery rates of the targets were 85.3%-108.8%. The relative standard deviations (RSDs, n=6) were 3.1%-9.4%. The established method was also employed for the analysis of cosmetics in the market, and octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) were detected at various levels in the cosmetics. The method established in this study has the advantages of operational simplicity, high sensitivity, and good reproducibility, and it allows for the determination of seven DMCs in cosmetics with different formulation systems. The establishment of this method provides a basis for the quality supervision and inspection of DMCs in cosmetics in China, in addition to providing technical support for follow-up health and safety evaluation.