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Title: Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment

Abstract

Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have large implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption frommore » 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of cellulose microfibril dimensions and crystallite size becomes more apparent. Further, this enlargement of cellulose microfibril dimensions is attributed to specific processes, including the co-crystallization of crystalline cellulose driven by irreversible inter-chain hydrogen bonding (similar to hornification) and/or cellulose annealing that converts amorphous cellulose to paracrystalline and crystalline cellulose. Essentially, lignin acts as a barrier to prevent cellulose crystallinity increase and cellulose fibril coalescence during DAP.« less

Authors:
 [1];  [2];  [1];  [3];  [3];  [3];  [4];  [5];  [3];  [6];  [5]
  1. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry
  2. Washington Univ., St. Louis, MO (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Structural Molecular Biology (CSMB)
  4. Univ. of California, Riverside, CA (United States). Bourns College of Engineering
  5. Univ. of California, Riverside, CA (United States). Bourns College of Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
  6. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1259860
Grant/Contract Number:  
FWP ERKP752; FWP ERKP291
Resource Type:
Accepted Manuscript
Journal Name:
Biotechnology for Biofuels
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 1754-6834
Publisher:
BioMed Central
Country of Publication:
United States
Language:
English
Subject:
60 APPLIED LIFE SCIENCES; Cellulose ultrastructure; Lignin content; Dilute acid pretreatment; Delignification; Enzymatic sugar release; Biomass recalcitrance

Citation Formats

Sun, Qining, Foston, Marcus, Meng, Xianzhi, Sawada, Daisuke, Pingali, Sai Venkatesh, O’Neill, Hugh M., Li, Hongjia, Wyman, Charles E., Langan, Paul, Ragauskas, Art J., and Kumar, Rajeev. Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment. United States: N. p., 2014. Web. doi:10.1186/s13068-014-0150-6.
Sun, Qining, Foston, Marcus, Meng, Xianzhi, Sawada, Daisuke, Pingali, Sai Venkatesh, O’Neill, Hugh M., Li, Hongjia, Wyman, Charles E., Langan, Paul, Ragauskas, Art J., & Kumar, Rajeev. Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment. United States. https://doi.org/10.1186/s13068-014-0150-6
Sun, Qining, Foston, Marcus, Meng, Xianzhi, Sawada, Daisuke, Pingali, Sai Venkatesh, O’Neill, Hugh M., Li, Hongjia, Wyman, Charles E., Langan, Paul, Ragauskas, Art J., and Kumar, Rajeev. Tue . "Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment". United States. https://doi.org/10.1186/s13068-014-0150-6. https://www.osti.gov/servlets/purl/1259860.
@article{osti_1259860,
title = {Effect of lignin content on changes occurring in poplar cellulose ultrastructure during dilute acid pretreatment},
author = {Sun, Qining and Foston, Marcus and Meng, Xianzhi and Sawada, Daisuke and Pingali, Sai Venkatesh and O’Neill, Hugh M. and Li, Hongjia and Wyman, Charles E. and Langan, Paul and Ragauskas, Art J. and Kumar, Rajeev},
abstractNote = {Obtaining a better understanding of the complex mechanisms occurring during lignocellulosic deconstruction is critical to the continued growth of renewable biofuel production. A key step in bioethanol production is thermochemical pretreatment to reduce plant cell wall recalcitrance for downstream processes. Previous studies of dilute acid pretreatment (DAP) have shown significant changes in cellulose ultrastructure that occur during pretreatment, but there is still a substantial knowledge gap with respect to the influence of lignin on these cellulose ultrastructural changes. This study was designed to assess how the presence of lignin influences DAP-induced changes in cellulose ultrastructure, which might ultimately have large implications with respect to enzymatic deconstruction efforts. Native, untreated hybrid poplar (Populus trichocarpa x Populus deltoids) samples and a partially delignified poplar sample (facilitated by acidic sodium chlorite pulping) were separately pretreated with dilute sulfuric acid (0.10 M) at 160°C for 15 minutes and 35 minutes, respectively . Following extensive characterization, the partially delignified biomass displayed more significant changes in cellulose ultrastructure following DAP than the native untreated biomass. With respect to the native untreated poplar, delignified poplar after DAP (in which approximately 40% lignin removal occurred) experienced: increased cellulose accessibility indicated by increased Simons’ stain (orange dye) adsorption from 21.8 to 72.5 mg/g, decreased cellulose weight-average degree of polymerization (DPw) from 3087 to 294 units, and increased cellulose crystallite size from 2.9 to 4.2 nm. These changes following DAP ultimately increased enzymatic sugar yield from 10 to 80%. We conclude that, overall, the results indicate a strong influence of lignin content on cellulose ultrastructural changes occurring during DAP. With the reduction of lignin content during DAP, the enlargement of cellulose microfibril dimensions and crystallite size becomes more apparent. Further, this enlargement of cellulose microfibril dimensions is attributed to specific processes, including the co-crystallization of crystalline cellulose driven by irreversible inter-chain hydrogen bonding (similar to hornification) and/or cellulose annealing that converts amorphous cellulose to paracrystalline and crystalline cellulose. Essentially, lignin acts as a barrier to prevent cellulose crystallinity increase and cellulose fibril coalescence during DAP.},
doi = {10.1186/s13068-014-0150-6},
journal = {Biotechnology for Biofuels},
number = 1,
volume = 7,
place = {United States},
year = {Tue Oct 14 00:00:00 EDT 2014},
month = {Tue Oct 14 00:00:00 EDT 2014}
}

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Cited by: 111 works
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Fibre size does not appear to influence the ease of enzymatic hydrolysis of organosolv-pretreated softwoods
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Characteristics of degraded cellulose obtained from steam-exploded wheat straw
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Cellulosic biorefineries—unleashing lignin opportunities
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Effect of Steam Treatment on the Properties of Wood Cell Walls
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Changes in the Structure of the Cellulose Fiber Wall during Dilute Acid Pretreatment in Populus Studied by 1 H and 2 H NMR
journal, October 2010

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  • Energy & Fuels, Vol. 24, Issue 10
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CPMAS carbon-13 NMR analysis of the crystal transformation induced for Valonia cellulose by annealing at high temperatures
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Structural changes of native cellulose crystals induced by annealing in aqueous alkaline and acidic solutions at high temperatures
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journal, January 2013

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  • Energy & Environmental Science, Vol. 6, Issue 3
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Biomass Characterization: Recent Progress in Understanding Biomass Recalcitrance
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In planta expression of A. cellulolyticus Cel5A endocellulase reduces cell wall recalcitrance in tobacco and maize
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  • Brunecky, Roman; Selig, Michael J.; Vinzant, Todd B.
  • Biotechnology for Biofuels, Vol. 4, Issue 1
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Cellulose accessibility limits the effectiveness of minimum cellulase loading on the efficient hydrolysis of pretreated lignocellulosic substrates
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  • Arantes, Valdeir; Saddler, Jack N.
  • Biotechnology for Biofuels, Vol. 4, Issue 1, Article No. 3
  • DOI: 10.1186/1754-6834-4-3

Assessing the molecular structure basis for biomass recalcitrance during dilute acid and hydrothermal pretreatments
journal, January 2013


Bioconversion of lignocellulose: inhibitors and detoxification
journal, January 2013

  • Jönsson, Leif J.; Alriksson, Björn; Nilvebrant, Nils-Olof
  • Biotechnology for Biofuels, Vol. 6, Issue 1
  • DOI: 10.1186/1754-6834-6-16

Lignin Depletion Enhances the Digestibility of Cellulose in Cultured Xylem Cells
journal, July 2013


Works referencing / citing this record:

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Physical and chemical differences between one-stage and two-stage hydrothermal pretreated hardwood substrates for use in cellulosic ethanol production
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Laccase mediated delignification of pineapple leaf waste: an ecofriendly sustainable attempt towards valorization
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Altered lignocellulose chemical structure and molecular assembly in CINNAMYL ALCOHOL DEHYDROGENASE-deficient rice
journal, November 2019


Isolation and Characterization of Novel Lignolytic, Cellulolytic, and Hemicellulolytic Bacteria from Wood-Feeding Termite Cryptotermes brevis
journal, July 2018

  • Tsegaye, Bahiru; Balomajumder, Chandrajit; Roy, Partha
  • International Microbiology, Vol. 22, Issue 1
  • DOI: 10.1007/s10123-018-0024-z

Characterization of lignin derived from water-only and dilute acid flowthrough pretreatment of poplar wood at elevated temperatures
journal, December 2015


Advances in understanding the surface chemistry of lignocellulosic biomass via time-of-flight secondary ion mass spectrometry
journal, December 2016

  • Tolbert, Allison; Ragauskas, Arthur J.
  • Energy Science & Engineering, Vol. 5, Issue 1
  • DOI: 10.1002/ese3.144

New perspective on glycoside hydrolase binding to lignin from pretreated corn stover
journal, December 2015

  • Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth
  • Biotechnology for Biofuels, Vol. 8, Issue 1
  • DOI: 10.1186/s13068-015-0397-6

Recent advances in understanding the pseudo-lignin formation in a lignocellulosic biorefinery
journal, January 2018

  • Shinde, Somnath D.; Meng, Xianzhi; Kumar, Rajeev
  • Green Chemistry, Vol. 20, Issue 10
  • DOI: 10.1039/c8gc00353j

Saccharification of pretreated sawdust by Aspergillus niger cellulase
journal, March 2015


Altered lignocellulose chemical structure and molecular assembly in CINNAMYL ALCOHOL DEHYDROGENASE-deficient rice
journal, November 2019


Laccase mediated delignification of pineapple leaf waste: an ecofriendly sustainable attempt towards valorization
journal, April 2019


Characterization of lignin derived from water-only and dilute acid flowthrough pretreatment of poplar wood at elevated temperatures
journal, December 2015


New perspective on glycoside hydrolase binding to lignin from pretreated corn stover
journal, December 2015

  • Yarbrough, John M.; Mittal, Ashutosh; Mansfield, Elisabeth
  • Biotechnology for Biofuels, Vol. 8, Issue 1
  • DOI: 10.1186/s13068-015-0397-6

Consolidated bioprocessing of Populus using Clostridium (Ruminiclostridium) thermocellum: a case study on the impact of lignin composition and structure
journal, February 2016

  • Dumitrache, Alexandru; Akinosho, Hannah; Rodriguez, Miguel
  • Biotechnology for Biofuels, Vol. 9, Issue 1
  • DOI: 10.1186/s13068-016-0445-x

Physical and chemical differences between one-stage and two-stage hydrothermal pretreated hardwood substrates for use in cellulosic ethanol production
journal, February 2016

  • Guilliams, Andrew; Pattathil, Sivakumar; Willies, Deidre
  • Biotechnology for Biofuels, Vol. 9, Issue 1
  • DOI: 10.1186/s13068-016-0446-9

Production of xylooligosaccharides and monosaccharides from poplar by a two-step acetic acid and peroxide/acetic acid pretreatment
journal, April 2019