Structural elucidation and targeted valorization of poplar lignin from the synergistic hydrothermal-deep eutectic...

Elucidating the structural variations of lignin during the pretreatment is very important for lignin valorization. Herein, poplar wood was pretreated with an integrated process, which was composed of AlCl₃-catalyzed hydrothermal pretreatment (HTP, 130-150 °C, 1.0 h) and mild deep-eutectic solvents (DES, 100 °C, 10 min) delignification for recycling lignin fractions. Confocal Raman Microscopy (CRM) was developed to visually monitor the delignification process during the HTP-DES pretreatment. NMR characterizations (2D-HSQC and ³¹P NMR) and elemental analysis demonstrated that the lignin fractions had undergone the following structural changes, such as dehydration, depolymerization, condensation. Molecular weights (GPC), microstructure (SEM and TEM), and antioxidant activity (DPPH analysis) of the lignins revealed that the DES delignification resulted in homogeneous lignin fragments (1.32 < PDI < 1.58) and facilitated the rapid assemblage of lignin nanoparticles (LNPs) with controllable nanoscale sizes (30-210 nm) and excellent antioxidant activity. These findings will enhance the understanding of structural transformations of the lignin during the integrated process and maximize the lignin valorization in a current biorefinery process.