Integrating DFT-assisted optimization into UPLC-DAD method development: simultaneous determination of six...

A robust UPLC-DAD method was established for the simultaneous determination of six bioactive compounds-atractylenolides I, II, III, atractylodin, atractylone, and β-eudesmol-from Atractylodes lancea and Atractylodes macrocephala Koidz in cosmetic matrices, addressing potential safety risks such as sensitization and toxicity. Density functional theory (DFT) calculations were employed to screen extraction solvents by evaluating the oxidation activity, thermochemical stability, photochemical stability, and hydrolysis tendency of the target molecules. For sample purification, a unified QuEChERS procedure utilizing silica (60 Å) was optimized, which effectively excluded strong adsorbents. Method validation confirmed satisfactory linearity (R² ≥ 0.9992) across specified concentration ranges, and demonstrated negligible matrix effects (slope ratios: 0.98-1.03) across diverse cosmetic matrices. Analysis of commercial products revealed detectable levels of atractylenolide III in some items, while overall contents of hazardous lactones and heterocyclic compounds were minimal or even below the detection limits (LODs), indicating a generally safe profile regarding the target compounds. Nevertheless, potential risks arising from variations in herbal material sources and extraction methodologies remain, highlighting the relevance of this reliable analytical approach for cosmetic safety surveillance.