Abstract

BackgroundCellulase adsorption to lignin is considered a cost barrier for bioethanol production; however, its detailed association mechanism is still not fully understood. In this study, two natural poplar variants with high and low sugar release performance were selected as the low and high recalcitrant raw materials (named L and H, respectively). Three different lignin fractions were extracted using ethanol, followed by p-dioxane and then cellulase treatment from the dilute acid pretreated poplar solids (fraction 1, 2, and 3, respectively).ResultsEach lignin fraction had different physicochemical properties. Ethanol-extracted lignin had the lowest weight average molecular weight, while the molecular weights for the other two lignin fractions were similar. 31P NMR analysis revealed that lignin fraction with higher molecular weight contained more aliphatic hydroxyl groups and less phenolic hydroxyl groups. Semi-quantitative analysis by 2D HSQC NMR indicated that the lignin fractions isolated from the natural variants had different contents of syringyl (S), guaiacyl (G) and interunit linkages. Lignin extracted by ethanol contained the largest amount of S units, the smallest amounts of G and p-hydroxybenzoate (PB) subunits, while the contents of these lignin subunits in the other two lignin fractions were similar. The lignin fraction obtained after cellulase treatment was primarily comprised of β-O-4 linkages with small amounts of β-5 and β–β linkages. The binding strength of these three lignin fractions obtained by Langmuir equations were in the order of L1 > L3 > L2 for the low recalcitrance poplar and H1 > H2 > H3 for the high recalcitrance poplar.ConclusionsOverall, adsorption ability of lignin was correlated with the sugar release of poplar. Structural features of lignin were associated with its binding to CBH. For natural poplar variants, lignin fractions with lower molecular weight and polydispersity index (PDI) exhibited more CBH adsorption ability. Lignins with more phenolic hydroxyl groups had higher CBH binding strength. It was also found that lignin fractions with more condensed aromatics adsorbed more CBH likely attributed to stronger hydrophobic interactions.

Highlights

  • Cellulase adsorption to lignin is considered a cost barrier for bioethanol production; its detailed association mechanism is still not fully understood

  • The Cellobiohydrolase I (CBH) adsorptions onto different lignin fractions from two Populus trichocarpa natural variants were investigated with the physicochemical properties of each lignin fractions

  • Molecular weight and polydispersity index (PDI) of lignin fractions were negatively correlated with CBH binding

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Summary

Introduction

Cellulase adsorption to lignin is considered a cost barrier for bioethanol production; its detailed association mechanism is still not fully understood. Lignin is a major component in the cell wall of terrestrial plants and usually constitutes about 15–30% of its total dry weight. It plays an important role in the structural integrity and protection from microorganism attack [1]. Increased research efforts have been conducted in this field to make biomass utilization economically and technically feasible [7] These studies have reported several important findings including the fact that a higher phenolic hydroxyl content can result in an increased lignin cellulase adsorption capacity [8,9,10], and a higher carboxylic acid group content of the associated lignin can enhance the enzymatic hydrolysis of lignocellulosic biomass [11, 12]. Further studies are needed to clarify the mechanisms leading to the inconsistent results

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