Biphasic phenoxyethanol‐acid pretreatment enhances bamboo hydrolysis via LCC cleavage and solvation

Abstract This research explores the fractionation efficiency and degradation mechanism of bamboo residues (BR) using a phenoxyethanol/sulfuric acid (EPH/H 2 SO 4 ) biphasic pretreatment. The experimental findings demonstrate that the EPH:acid ratio notably improves component separation. The lignin‐carbohydrate complexes (LCC) removal reached 62.9%, and the 72 h enzymatic hydrolysis yield rose to 39.6% at a ratio of 4:1. 2D HSQC NMR analysis verified that phenyl glycoside and benzyl ether linkages were the principal degradation sites. Molecular dynamics (MD) simulations and density functional theory (DFT) calculations revealed a synergistic mechanism for LCC removal. It was indicated that EPH enlarged the solvent‐accessible surface area of LCCs, promoting solvation via van der Waals interactions. DFT analysis illustrated that H 3 O + facilitates bond cleavage through protonation‐induced polarization, whereas EPH stabilizes the resulting intermediates through hydrogen bonding and π–π interactions. This integrated experimental and computational approach offers a theoretical basis for optimizing organic biphasic systems for efficient lignocellulosic bioconversion.