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Profiling of polyphenolics in four types of brown macroalgae, namely Laminaria japonica ( L. japonica ), Undaria pinnatifida ( U. pinnatifida ), Sargassum fusiforme ( S. fusiforme ), and Ascophyllum nodosum ( A. nodosum ), and their effect on oxidation resistance were investigated for the first time. Polyphenolic extracts from marine brown macroalgae were shown to effectively remove oxidants from cells and cellular systems. A. nodosum showed the highest antioxidant activity among evaluated brown macroalgae, showing a better scavenging effect on 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical and alleviating oxidative damage caused by hydrogen peroxide to human keratinocytes (HaCaT) cells. Through Q-Exactive HF-X mass spectrometry analysis, 12 polyphenolic compounds were preliminarily identified, including phlorotannins, phenolic acids, and flavonoids. Significant differences in content and variety of polyphenolics were found in evaluated brown macroalgae, which could be related to differences in antioxidant activity in vivo and in vitro. Moreover, the antioxidant activity might be related to the total phenolic content and the types of polyphenolics, especially phlorotannins. The findings presented in this study indicate that A. nodosum could be used as an important substitute for functional ingredients in foods and pharmaceutical preparations, as well as a raw material for phlorotannins research.

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Metabolomic Approach for Characterization of Polyphenolic Compounds in Laminaria japonica, Undaria pinnatifida, Sargassum fusiforme and Ascophyllum nodosum