Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production.

Sajal Kanti Dutta,Saikat Chakraborty

doi:10.1038/srep38173

Abstract

Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale–the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80–90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5–6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation.

Highlights

Sugars) out of the pores into the bulk phase[19]
The sequence of length of scales participating in the multi-scale enzymatic hydrolysis of long-chain porous hemicelluloses such as beechwood/hardwood/softwood xylan, arabinoxylan, etc., is: Reactor Scale >Molecular Scale >Pore Scale
We show that the secret to rapidly producing soluble sugars from amorphous natural polymers such as hemicelluloses lies in their smallest scale–the pores

Summary

Introduction

Sugars) out of the pores into the bulk phase[19] These solid phase reactions are followed by liquid phase enzymatic hydrolysis of the soluble sugars to the monomers. Most multi-scale reactive processes constitute of three representative scales, namely, the macro-scale (reactor), the meso-scale (pore), and the micro-scale (molecular), with the smallest (molecular) scale often being the most important determinant of the reaction rate. The sequence of length of scales participating in the multi-scale enzymatic hydrolysis of long-chain porous hemicelluloses such as beechwood/hardwood/softwood xylan, arabinoxylan, etc., is: Reactor Scale >Molecular Scale >Pore Scale. This work is guided by the premise that the transport and reaction processes that determine product yields in enzymatic hydrolysis of amorphous natural polymers (such as xylan), where the pore-scale is the smallest of the three representative scales, are fundamentally different from other multi-scale catalytic reactions where the molecular scale is the smallest. We show that the secret to rapidly producing soluble sugars from amorphous natural polymers such as hemicelluloses lies in their smallest scale–the pores

Methods

Results

Conclusion