Quantitative analysis of hormones in cosmetics by LC-MS/MS combined with an advanced calibration model

Abstract

In this contribution, tandem mass spectrometry coupled with liquid chromatography (LC-MS/MS) was combined with the multiplicative effects model for mass spectroscopy (MEM_MS) to quantitatively determine three hormones (i.e. estrone, hydrocortisone and progesterone) in cosmetics (toner and essence emulsion). The adoption of the MEM_MS model in the analysis of LC-MS/MS data was to address the problem of sensitivity and signal instability of LC-MS/MS over time caused by the gradual fouling of the ion source, vacuum instability, drifting of baseline, ion suppression, etc. Experimental results showed that the MEM_MS model could effectively mitigate the detrimental effects of the signal instability of LC-MS/MS over time, and achieve quite accurate quantitative results for estrone, hydrocortisone, and progesterone in both toner and essence emulsion samples with average relative prediction error values no larger than 10.0%, which were far lower than the corresponding values (11.5–67.4%) of the conventional univariate internal standard calibration method based on peak height ratios between the peak of the target analytes and that of the internal standard.