Fuel, cilt.415, 2026 (SCI-Expanded, Scopus)
The valorization of agro-industrial residues via enzymatic hydrolysis represents a sustainable route for second-generation bioethanol production. However, hydrolytic efficiency is frequently limited by enzyme deactivation and non-productive binding of enzymes to lignin. In this study, nine novel homopolymers and block copolymers with varying charged and neutral units were evaluated as performance enhancers to improve enzyme-substrate interactions and reduce lignin-associated inhibition. Structural and compositional changes of raw apple pomace, polymer-free, and polymer-containing samples were analyzed using fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA), providing mechanistic insight into polymer-assisted hydrolysis. Among all tested polymers, Poly[3-dimethyl(methacryloyloxyethyl)ammonium propane sulfonate]- bl[ock -poly(methyl methacrylate) (PβDMA- b -PMMA, P1) significantly increased enzymatic activity, sugar release, and glucan conversion. Specifically, P1 led to a 27.3% increase in reducing sugar concentration, a 25.6% increase in ethanol titer (Y P/Smax: 0.43 g/g; Qpmax: 1.00 g/L.h), and a 13% improvement in glucan conversion efficiency (60.6%) during separate hydrolysis and fermentation (SHF). Simultaneous saccharification and fermentation (SSF) using 0.5% w/v P1 and 15% apple pomace resulted in a bioethanol concentration of 63.3 g/L, compared to 56.7 g/L in the polymer-free control when Kluyveromyces marxianus was employed. These findings demonstrate the synergistic effect of polymer additives in enhancing both hydrolytic efficiency and fermentation productivity. The mechanistic insights gained suggest that rationally designed polymeric additives provide an effective strategy to overcome substrate recalcitrance, offering a promising approach for sustainable second-generation biofuel production.