A facile one-pot spray-drying process was developed for fabrication and in-situ crosslinking of chitosan microspheres to improve the adsorption capacity by microscopic design. A fully biobased nature was achieved by utilizing genipin (GP) as a crosslinking agent and chitosan derived nano-graphene oxide (nGO) as a property tuner. The produced chitosan microspheres were further proven as powerful adsorbents for common wastewater contaminants such as anionic dyes and pharmaceutical contaminants, here modelled by methyl orange (MO) and diclofenac sodium (DCF). By regulating the amount of GP and nGO, as well as by controlling the process parameters including the spraydrying inlet temperature and post-heat treatment, the surface morphology, size, zeta potential and adsorption efficiency of the microspheres could be tuned accordingly. The adsorption efficiency for MO and DCF reached 98.9 and 100 %, respectively. The microspheres retained high DCF adsorption efficiency after six adsorption and desorption cycles and the recyclability was improved by incorporated nGO. The fabricated microspheres, thus, have great potential as reusable and eco-friendly adsorbents.

Two methods with different cross-linking mechanisms for designing hemicellulose-based full interpenetrating polymer networks (IPNs) were developed through the sequential synthesis of full IPNs from O-acetyl-galactoglucomannan (AcGGM) utilizing free-radical polymerization and a thiol-ene click reaction. A faster swelling rate was observed for all IPN formulations compared with the single-network gels. The highly porous structure of the IPNs with small interconnected pores was verified using scanning electron microscopy. A rheological analysis revealed that the AcGGM IPNs fabricated by the free-radical polymerization of acrylamide and N-N'-methylenebisacrylamide (cross-linker) had shear storage modulus (G') values approximately 5 and 2.5 times higher than that of the corresponding precursor single networks of AcGGM. IPNs achieved through thiol-ene reactions between thiolated AcGGM and polyethylene glycol diacrylate had G' values 35-40 times higher than the single-network reference hydrogels.

The family of hemicelluloses stands out as a very promising natural resource that can be utilized as a biobased materials feedstock. An in-depth understanding of the hemicellulose inherent structural and property features as well as the structure property relationships induced by the specific supramolecular hierarchical organization of lignocellulosic biopolymers will be a key enabling technology in the emerging biorefinery sector. This Review aims to give a perspective on these issues and demonstrate how the transfer of molecular wood cell interactions into hemicellulose-based materials may offer new design principles for material formulations.