In the cosmetics industry, various natural complex mixtures such as botanical extracts and essential oils are used. In addition, finished consumer products may contain a number of constituents of natural origin but many products are derived from organic synthesis too. Hence, finding skin sensitizers within this myriad of chemicals is an arduous task. Nowadays, methods validated by European dedicated instances to evaluate the allergenicity of chemicals are incapable of predicting the sensitization potential of complex mixtures, although research has progressed a lot in this direction recently. In this context, precisely identifying the culprit(s) responsible for skin sensitization in these mixtures is essential for risk assessment. This review is a short summary of approaches that identify allergens in chemical mixtures such as bioassay-guided chemical fractionation, structure–activity relationship studies, and recent methods allowing identification of reactive intermediates in natural extracts exposed to air oxidation. It is shown that substantial progress has been made, although the identification of sensitizers in complex mixtures continues to be puzzling.
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