A Novel HILIC‐UPLC‐DAD‐MS/MS Method for the Analysis of Mycosporine‐Like Amino Acids and Their Quantification in Diverse Algae

Mycosporine-like amino acids (MAAs) are photoprotective compounds primarily produced by marine organisms, especially red algae. Chemically, MAAs and their precursors are low-molecular-weight natural products that absorb ultraviolet radiation in the range of 270-360 nm without generating free radicals. Owing to these properties, MAAs have attracted considerable interest for potential pharmaceutical and cosmetic applications as natural sunscreen agents. In this study, the first hydrophilic interaction liquid chromatography-ultra-performance liquid chromatography (HILIC-UPLC) method, coupled with both diode array detector (DAD) and tandem mass spectrometry (MS/MS), was developed for the determination of 11 MAAs and 2 MAA precursors in various algal species. As column, a YMC-Triart Diol-HILIC (particle size: 1.9 µm) was used, and the separation of the MAAs realized in under 5 min. The validation of the method was carried out following International Council for Harmonisation (ICH) guidelines, demonstrating linearity, selectivity, precision, and accuracy. The analysis of extracts prepared from well-known species, such as Porphyra sp. and Chondrus crispus, confirmed practical applicability. Demonstrating feasibility of MS/MS-based quantification of co-eluting compounds, the method represents an appealing alternative that surpasses established procedures not only in terms of analysis time but also by providing a substantially increased informative value.