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Parallel experiments run on natural and bioinspired model phenolic polymers suggested that these structural modifications positively impacted on the antioxidant properties of lignins and hydrolyzable tannins, whereas significant degradation of condensed tannin moieties occurred, likely responsible for the lowering of the reducing power observed for grape pomace and pecan nut shell. These results open new perspectives toward the exploitation and manipulation of agri-food byproducts for application as antioxidant additives in functional mat