Valorization of Food Waste and Marine Biomass into 5-(Hydroxymethyl)furfurylamine through the Sustainable Chemobiocatalytic Strategy

Abstract A single-vessel two-step chemobiocatalytic strategy was developed for conversion of d-fructose, bread crumbs, and marine biomass (purple laver) into value-added furanic chemicals. A ternary deep eutectic solvent (DES), Be/Gly/MaA, efficiently catalyzed 5-hydroxymethylfurfural (5-HMF) production from d-fructose, bread crumbs, and purple laver, achieving a 51.9% yield, a productivity of 0.23 g 5-HMF/(g bread crumbs), and a maximum yield of 39.9%, respectively. The resulting 5-HMF was further upgraded through the selective biotransformation by an engineered Escherichia coli expressing a SpyTag/SpyCatcher-cyclized ω-transaminase (CvTA). The biocatalyst exhibited enhanced tolerance to both the Be/Gly/MaA and 5-HMF, enabling efficient synthesis of 5-(hydroxymethyl)furfurylamine (HMFA) with l-alanine as the amine donor. HMFA was produced directly from all three feedstocks without intermediate purification. Crude 5-HMF derived from food waste and marine biomass was further upgraded to 2,5-bis(hydroxymethyl)furan, 2,5-diformylfuran, 2,5-furandicarboxylic acid, and 5-formyl-2-furoic acid via enzymatic pathways. This work establishes a modular platform for sustainable biomass valorization through integrated chemobiocatalysis.