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Title: Cellulose-Hemicellulose Interactions at Elevated Temperatures Increase Cellulose Recalcitrance to Biological Conversion

Abstract

It has been previously shown that cellulose-lignin droplets' strong interactions, resulting from lignin coalescence and redisposition on cellulose surface during thermochemical pretreatments, increase cellulose recalcitrance to biological conversion, especially at commercially viable low enzyme loadings. However, information on the impact of cellulose-hemicellulose interactions on cellulose recalcitrance following relevant pretreatment conditions are scarce. Here, to investigate the effects of plausible hemicellulose precipitation and re-association with cellulose on cellulose conversion, different pretreatments were applied to pure Avicel(R) PH101 cellulose alone and Avicel mixed with model hemicellulose compounds followed by enzymatic hydrolysis of resulting solids at both low and high enzyme loadings. Solids produced by pretreatment of Avicel mixed with hemicelluloses (AMH) were found to contain about 2 to 14.6% of exogenous, precipitated hemicelluloses and showed a remarkably much lower digestibility (up to 60%) than their respective controls. However, the exogenous hemicellulosic residues that associated with Avicel following high temperature pretreatments resulted in greater losses in cellulose conversion than those formed at low temperatures, suggesting that temperature plays a strong role in the strength of cellulose-hemicellulose association. Molecular dynamics simulations of hemicellulosic xylan and cellulose were found to further support this temperature effect as the xylan-cellulose interactions were found to substantially increase atmore » elevated temperatures. Furthermore, exogenous, precipitated hemicelluloses in pretreated AMH solids resulted in a larger drop in cellulose conversion than the delignified lignocellulosic biomass containing comparably much higher natural hemicellulose amounts. Increased cellulase loadings or supplementation of cellulase with xylanases enhanced cellulose conversion for most pretreated AMH solids; however, this approach was less effective for solids containing mannan polysaccharides, suggesting stronger association of cellulose with (hetero) mannans or lack of enzymes in the mixture required to hydrolyze such polysaccharides.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [4];  [2];  [5];  [6];  [3];  [3];  [2]
  1. National Renewable Energy Laboratory (NREL), Golden, CO (United States)
  2. University of California, Riverside; Oak Ridge National Laboratory
  3. Oak Ridge National Laboratory; University of Tennessee
  4. Michigan Technological University
  5. University of Houston
  6. Michigan State University
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Office of Biological and Environmental Research
OSTI Identifier:
1427354
Report Number(s):
NREL/JA-2700-71138
Journal ID: ISSN 1463-9262; GRCHFJ
DOE Contract Number:  
AC36-08GO28308
Resource Type:
Journal Article
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; Journal Issue: 4; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 59 BASIC BIOLOGICAL SCIENCES; hemicellulose; cellulose; recalcitrance; pretreatment; enzymatic hydrolysis

Citation Formats

Mittal, Ashutosh, Himmel, Michael E, Kumar, Rajeev, Smith, Micholas Dean, Petridis, Loukas, Ong, Rebecca G., Cai, Charles M., Balan, Venkatesh, Dale, Bruce E., Ragauskas, Arthur J., Smith, Jeremy C., and Wyman, Charles E. Cellulose-Hemicellulose Interactions at Elevated Temperatures Increase Cellulose Recalcitrance to Biological Conversion. United States: N. p., 2018. Web. doi:10.1039/C7GC03518G.
Mittal, Ashutosh, Himmel, Michael E, Kumar, Rajeev, Smith, Micholas Dean, Petridis, Loukas, Ong, Rebecca G., Cai, Charles M., Balan, Venkatesh, Dale, Bruce E., Ragauskas, Arthur J., Smith, Jeremy C., & Wyman, Charles E. Cellulose-Hemicellulose Interactions at Elevated Temperatures Increase Cellulose Recalcitrance to Biological Conversion. United States. doi:10.1039/C7GC03518G.
Mittal, Ashutosh, Himmel, Michael E, Kumar, Rajeev, Smith, Micholas Dean, Petridis, Loukas, Ong, Rebecca G., Cai, Charles M., Balan, Venkatesh, Dale, Bruce E., Ragauskas, Arthur J., Smith, Jeremy C., and Wyman, Charles E. Tue . "Cellulose-Hemicellulose Interactions at Elevated Temperatures Increase Cellulose Recalcitrance to Biological Conversion". United States. doi:10.1039/C7GC03518G.
@article{osti_1427354,
title = {Cellulose-Hemicellulose Interactions at Elevated Temperatures Increase Cellulose Recalcitrance to Biological Conversion},
author = {Mittal, Ashutosh and Himmel, Michael E and Kumar, Rajeev and Smith, Micholas Dean and Petridis, Loukas and Ong, Rebecca G. and Cai, Charles M. and Balan, Venkatesh and Dale, Bruce E. and Ragauskas, Arthur J. and Smith, Jeremy C. and Wyman, Charles E.},
abstractNote = {It has been previously shown that cellulose-lignin droplets' strong interactions, resulting from lignin coalescence and redisposition on cellulose surface during thermochemical pretreatments, increase cellulose recalcitrance to biological conversion, especially at commercially viable low enzyme loadings. However, information on the impact of cellulose-hemicellulose interactions on cellulose recalcitrance following relevant pretreatment conditions are scarce. Here, to investigate the effects of plausible hemicellulose precipitation and re-association with cellulose on cellulose conversion, different pretreatments were applied to pure Avicel(R) PH101 cellulose alone and Avicel mixed with model hemicellulose compounds followed by enzymatic hydrolysis of resulting solids at both low and high enzyme loadings. Solids produced by pretreatment of Avicel mixed with hemicelluloses (AMH) were found to contain about 2 to 14.6% of exogenous, precipitated hemicelluloses and showed a remarkably much lower digestibility (up to 60%) than their respective controls. However, the exogenous hemicellulosic residues that associated with Avicel following high temperature pretreatments resulted in greater losses in cellulose conversion than those formed at low temperatures, suggesting that temperature plays a strong role in the strength of cellulose-hemicellulose association. Molecular dynamics simulations of hemicellulosic xylan and cellulose were found to further support this temperature effect as the xylan-cellulose interactions were found to substantially increase at elevated temperatures. Furthermore, exogenous, precipitated hemicelluloses in pretreated AMH solids resulted in a larger drop in cellulose conversion than the delignified lignocellulosic biomass containing comparably much higher natural hemicellulose amounts. Increased cellulase loadings or supplementation of cellulase with xylanases enhanced cellulose conversion for most pretreated AMH solids; however, this approach was less effective for solids containing mannan polysaccharides, suggesting stronger association of cellulose with (hetero) mannans or lack of enzymes in the mixture required to hydrolyze such polysaccharides.},
doi = {10.1039/C7GC03518G},
journal = {Green Chemistry},
issn = {1463-9262},
number = 4,
volume = 20,
place = {United States},
year = {2018},
month = {1}
}

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Effect of enzyme supplementation at moderate cellulase loadings on initial glucose and xylose release from corn stover solids pretreated by leading technologies
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