Diluting modulation-based two dimensional-liquid chromatography coupled with mass spectrometry for simultaneously determining multiclass prohibited substances in cosmetics

Abstract

Developing efficient and comprehensive screening methods for prohibited substances in cosmetics is critical for ensuring the quality and safety of cosmetics used in everyday life. This study proposed a heart-cutting two-dimensional liquid chromatography-mass spectrometry (2D-LC-MS) method based on online diluting modulation for detecting multiclass prohibited substances in cosmetics. The 2D-LC-MS method combines HILIC and RPLC techniques. Compounds near the dead time that the first dimensional HILIC could not separate were transferred to the second dimensional RPLC by valve switch, achieving good separation with a wide range of polarities. Moreover, the online diluting modulation solved the problem of mobile phase incompatibility, realizing an excellent column-head focusing effect and reducing the loss of sensitivity. Besides, the first dimensional analysis did not restrict the flow rate of the second dimensional analysis owing to the diluting modulation. We demonstrated the 2D-LC-MS system by determining 126 prohibited substances in cosmetic products, including hormones, local anesthetics, anti-infectives, adrenergic agents, antihistamines, pesticides, and other chemicals. All correlation coefficients of the compounds were above 0.9950. The LODs and the LOQs ranged from 0.000259 ng/mL to 16.6 ng/mL and 0.000864 ng/mL to 55.3 ng/mL, respectively. The RSDs% for intra-day and inter-day precision were within 6% and 14%, respectively. Compared with conventional one-dimensional liquid chromatography methods, the established method expanded the analytical coverage of cosmetics-prohibited substances with reduced matrix effects for most compounds and improved sensitivity for polar analytes. The results indicated that the 2D-LC-MS method was a powerful tool for screening multiclass prohibited substances in cosmetics.