Carbocatalysed hydrolytic cleaving of the glycosidic bond in fucoidan under microwave irradiation

Biomass valorization involves breaking down naturally occurring long chain polysaccharides into their constituent monomers. The polysaccharide chain consists of monomers adjoined via C (carbon)–O (oxygen) glycosidic linkages that are typically cleaved via hydrolytic scission. In this study, we aimed to recover fucose from the polysaccharide fucoidan, which can be extracted from seaweed biomass. We investigated the depolymerisation behavior of fucoidan sourced from two different species of seaweeds, namely Undaria pinnatifida (F-UP) and Fucus vesiculosus (F-FV). Catalytic depolymerisation experiments were performed using four different carbon-based catalysts – graphene, multiwalled carbon nanotubes (MWCNT), graphene oxide (GO), and reduced graphene oxide (rGO) – under microwave (MW) irradiation. Our results showed that the depolymerisation of fucoidan was best achieved using GO, which was attributed to the abundance of oxygen functionalities on its surface. Furthermore, based on gel permeation chromatography analyses, the depolymerisation of fucoidan was found to follow a two-step process: (1) random scission leading to the production of short-chain oligosaccharides and (2) acid-catalysed hydrolysis of the oligosaccharides to fucose. Because of the longer chain length of F-UP (61 kDa), the highest fucose yield of 17.4% using this species was obtained at a higher temperature of 120 °C in a closed vessel. Meanwhile, in the case of F-FV (1.1 kDa), the highest yield of 54.0% was obtained under reflux conditions at a lower temperature of 104 °C. Our mechanistic study based on semi-empirical quantum calculations also revealed that the recovery of fucose from F-FV is more energetically favoured than from F-UP as a result of their structural differences.