To investigate the interplay between substrate structure and enzymatic hydrolysis (EH) efficiency, poplar was pretreated with acidic sodium-chlorite (ASC), 3 % sodium-hydroxide (3-SH), and 3 % sulfuric acid (3-SA), resulting in different glucose yields of 94.10 %, 74.35 %, and 24.51 %, respectively, of pretreated residues. Residues were fractionated into cellulose, lignin and unhydrolyzed residue after EH (for lignin-carbohydrate complex (LCC) analysis) and analyzed using HPLC, FTIR, XPS, CP MAS 13C NMR and 2D-NMR (Lignin and LCC analysis). After delignification, holocellulose exhibited a dramatic increase in glucose yield (74.35 % to 90.82 % for 3-SH and 24.51 % to 80.0 % for 3-SA). Structural analysis of holocellulose suggested the synergistic interplay among cellulose allomorphs to limit glucose yield. Residual lignin analysis from un/pretreated residues indicated that higher β-β' contents and S/G ratios were favorable to the inhibitory effect but unfavourable to the holocellulose digestibility and followed the trend in the following order: 3-SA (L3) > 3-SH (L2) > native-lignin (L1). Analysis of enzymatically unhydrolyzed pretreated residues revealed the presence of benzyl ether (BE1,2) LCC and phenyl glycoside (PG) bond linking to xylose (X) and mannose (M), which yielded a xylan-lignin-glucomannan network. The stability, steric hindrance and hydrophobicity of this network may play a central role in defining poplar recalcitrance.
Keywords: Biomass recalcitrance; Cellulose; Enzymatic hydrolysis; Lignin condensation; Lignin-carbohydrate complex (LCC); Xylan-lignin-glucomannan.
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