DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Nature of Hololignin

Abstract

Acid chlorite delignification is frequently used to obtain a mixture of cellulose and hemicellulose known as holocellulose from biomass. While a majority of lignin is removed after holocellulose pulping, there appears to be a minor fraction of lignin that is more resistant to acid chlorite treatment and remains in the holocellulose even after repeated delignification treatment. This type of lignin, defined as hololignin, has not been characterized, is likely to contribute to biomass recalcitrance and is clearly of fundamental interest to understand its structural characteristics. In this study, hololignin isolated from poplar holocellulose was characterized with a wide array of techniques including GPC, quantitative 13C, DEPT-135, HSQC, and 31P NMR. The results were then compared to those from milled wood lignin (MWL), the representative native lignin isolated from poplar. NMR analysis demonstrated a depletion of cinnamyl aldehyde, acetyl group, and decrease of p-hydroxybenzoate structural units in hololignin. An enrichment of condensed structures in hololignin was observed. Hololignin also had a significantly lower molecular weight than MWL. Finally, hololignin is relatively enriched in guaiacyl units and has a lower S/G ratio, lower β-O-4 ether linkages, fewer aliphatic and phenolic hydroxyl groups, and more carboxylic acid groups than MWL.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [2];  [4]; ORCiD logo [5]
  1. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division
  3. Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemistry and Biochemistry
  4. Fujian Agriculture and Forestry Univ., Fuzhou (China). College of Material Engineering
  5. Univ. of Tennessee, Knoxville, TN (United States). Center of Renewable Carbon, Inst. of Agriculture and Dept. of Chemical and Biomolecular Engineering and Dept. of Forestry, Wildlife and Fisheries; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Biosciences Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1427613
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
ACS Sustainable Chemistry & Engineering
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2168-0485
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Acid chlorite; Delignification; Holocellulose pulping; Hololignin; Milled wood lignin

Citation Formats

Meng, Xianzhi, Pu, Yunqiao, Sannigrahi, Poulomi, Li, Mi, Cao, Shilin, and Ragauskas, Arthur J. The Nature of Hololignin. United States: N. p., 2017. Web. doi:10.1021/acssuschemeng.7b03285.
Meng, Xianzhi, Pu, Yunqiao, Sannigrahi, Poulomi, Li, Mi, Cao, Shilin, & Ragauskas, Arthur J. The Nature of Hololignin. United States. https://doi.org/10.1021/acssuschemeng.7b03285
Meng, Xianzhi, Pu, Yunqiao, Sannigrahi, Poulomi, Li, Mi, Cao, Shilin, and Ragauskas, Arthur J. Tue . "The Nature of Hololignin". United States. https://doi.org/10.1021/acssuschemeng.7b03285. https://www.osti.gov/servlets/purl/1427613.
@article{osti_1427613,
title = {The Nature of Hololignin},
author = {Meng, Xianzhi and Pu, Yunqiao and Sannigrahi, Poulomi and Li, Mi and Cao, Shilin and Ragauskas, Arthur J.},
abstractNote = {Acid chlorite delignification is frequently used to obtain a mixture of cellulose and hemicellulose known as holocellulose from biomass. While a majority of lignin is removed after holocellulose pulping, there appears to be a minor fraction of lignin that is more resistant to acid chlorite treatment and remains in the holocellulose even after repeated delignification treatment. This type of lignin, defined as hololignin, has not been characterized, is likely to contribute to biomass recalcitrance and is clearly of fundamental interest to understand its structural characteristics. In this study, hololignin isolated from poplar holocellulose was characterized with a wide array of techniques including GPC, quantitative 13C, DEPT-135, HSQC, and 31P NMR. The results were then compared to those from milled wood lignin (MWL), the representative native lignin isolated from poplar. NMR analysis demonstrated a depletion of cinnamyl aldehyde, acetyl group, and decrease of p-hydroxybenzoate structural units in hololignin. An enrichment of condensed structures in hololignin was observed. Hololignin also had a significantly lower molecular weight than MWL. Finally, hololignin is relatively enriched in guaiacyl units and has a lower S/G ratio, lower β-O-4 ether linkages, fewer aliphatic and phenolic hydroxyl groups, and more carboxylic acid groups than MWL.},
doi = {10.1021/acssuschemeng.7b03285},
journal = {ACS Sustainable Chemistry & Engineering},
number = 1,
volume = 6,
place = {United States},
year = {2017},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007

  • Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.
  • Science, Vol. 315, Issue 5813, p. 804-807
  • DOI: 10.1126/science.1137016

Biomass Characterization: Recent Progress in Understanding Biomass Recalcitrance
journal, August 2012

  • Foston, Marcus; Ragauskas, Arthur J.
  • Industrial Biotechnology, Vol. 8, Issue 4
  • DOI: 10.1089/ind.2012.0015

Investigating plant cell wall components that affect biomass recalcitrance in poplar and switchgrass
journal, January 2013

  • DeMartini, Jaclyn D.; Pattathil, Sivakumar; Miller, Jeffrey S.
  • Energy & Environmental Science, Vol. 6, Issue 3
  • DOI: 10.1039/c3ee23801f

Differences in the adsorption of enzymes onto lignins from diverse types of lignocellulosic biomass and the underlying mechanism
journal, January 2014


Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective
journal, December 2015


Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015


Preparation of sulfomethylated softwood kraft lignin as a dispersant for cement admixture
journal, January 2015


Value-adding to cellulosic ethanol: Lignin polymers
journal, March 2011

  • Doherty, William O. S.; Mousavioun, Payam; Fellows, Christopher M.
  • Industrial Crops and Products, Vol. 33, Issue 2
  • DOI: 10.1016/j.indcrop.2010.10.022

Towards lignin-based functional materials in a sustainable world
journal, January 2016

  • Kai, Dan; Tan, Mein Jin; Chee, Pei Lin
  • Green Chemistry, Vol. 18, Issue 5
  • DOI: 10.1039/C5GC02616D

Delignification of bamboo (Bambusa procera acher)
journal, January 2004


Alkaline peroxide pretreatment of corn stover: effects of biomass, peroxide, and enzyme loading and composition on yields of glucose and xylose
journal, January 2011

  • Banerjee, Goutami; Car, Suzana; Scott-Craig, John S.
  • Biotechnology for Biofuels, Vol. 4, Issue 1
  • DOI: 10.1186/1754-6834-4-16

Extraction of hemicellulose by hot water to reduce adsorbable organic halogen formation in chlorine dioxide bleaching of bagasse pulp
journal, February 2017


Oxygen Delignification Chemistry and Its Impact on Pulp Fibers
journal, January 2003

  • Yang, Rallming; Lucia, Lucian; Ragauskas, Arthur J.
  • Journal of Wood Chemistry and Technology, Vol. 23, Issue 1
  • DOI: 10.1081/WCT-120018613

Alkaline Peroxide Delignification of Corn Stover
journal, June 2017


Effect of acid-chlorite delignification on cellulose degree of polymerization
journal, October 2010


Lignin as Determined by Oxidation with Sodium Chlorite and a Comparison with Permanganate Lignin
journal, August 1978


A Model for Chlorine Dioxide Delignification of Chemical Pulp
journal, August 2010

  • Tarvo, Ville; Lehtimaa, Tuula; Kuitunen, Susanna
  • Journal of Wood Chemistry and Technology, Vol. 30, Issue 3
  • DOI: 10.1080/02773810903461476

The chemistry of delignification in pulp bleaching
journal, January 1962


Chemical reactions in chlorine dioxide stages of pulp bleaching: Intermediately formed hypochlorous acid
journal, January 1983

  • Kolar, J. J.; Lindgren, B. O.; Pettersson, Birgitta
  • Wood Science and Technology, Vol. 17, Issue 2
  • DOI: 10.1007/BF00369129

Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies
journal, September 2009


Removal of Wood Components During Chlorite Delignification of Black Spruce
journal, April 1971

  • Ahlgren, P. A.; Goring, D. A. I.
  • Canadian Journal of Chemistry, Vol. 49, Issue 8
  • DOI: 10.1139/v71-207

Characterization of Miscanthus giganteus Lignin Isolated by Ethanol Organosolv Process under Reflux Condition
journal, August 2012

  • Bauer, Stefan; Sorek, Hagit; Mitchell, Valerie D.
  • Journal of Agricultural and Food Chemistry, Vol. 60, Issue 33
  • DOI: 10.1021/jf302409d

Structural Characterization of Lignin during Pinus taeda Wood Treatment with Ceriporiopsis subvermispora
journal, July 2004


Cellulose Isolation Methodology for NMR Analysis of Cellulose Ultrastructure
journal, November 2011

  • Foston, Marcus B.; Hubbell, Chistopher A.; Ragauskas, Art J.
  • Materials, Vol. 4, Issue 11
  • DOI: 10.3390/ma4111985

Modification of the Lignin Structure during Alkaline Delignification of Eucalyptus Wood by Kraft, Soda-AQ, and Soda-O 2 Cooking
journal, October 2013

  • Prinsen, Pepijn; Rencoret, Jorge; Gutiérrez, Ana
  • Industrial & Engineering Chemistry Research, Vol. 52, Issue 45
  • DOI: 10.1021/ie401364d

A review of whole cell wall NMR by the direct-dissolution of biomass
journal, January 2016

  • Foston, Marcus; Samuel, Reichel; He, Jian
  • Green Chemistry, Vol. 18, Issue 3
  • DOI: 10.1039/C5GC02828K

Solid-state NMR characterization of switchgrass cellulose after dilute acid pretreatment
journal, January 2010

  • Samuel, Reichel; Pu, Yunqiao; Foston, Marcus
  • Biofuels, Vol. 1, Issue 1
  • DOI: 10.4155/bfs.09.17

A Comprehensive Approach for Quantitative Lignin Characterization by NMR Spectroscopy
journal, April 2004

  • Capanema, Ewellyn A.; Balakshin, Mikhail Y.; Kadla, John F.
  • Journal of Agricultural and Food Chemistry, Vol. 52, Issue 7
  • DOI: 10.1021/jf035282b

Quantitative Characterization of a Hardwood Milled Wood Lignin by Nuclear Magnetic Resonance Spectroscopy
journal, December 2005

  • Capanema, Ewellyn A.; Balakshin, Mikhail Yu.; Kadla, John F.
  • Journal of Agricultural and Food Chemistry, Vol. 53, Issue 25, p. 9639-9649
  • DOI: 10.1021/jf0515330

Quantitative 13 C NMR Analysis of Lignins with Internal Standards
journal, August 2001

  • Xia, Zhicheng; Akim, Leonid G.; Argyropoulos, Dimitris S.
  • Journal of Agricultural and Food Chemistry, Vol. 49, Issue 8
  • DOI: 10.1021/jf010333v

NMR Characterization of C3H and HCT Down-Regulated Alfalfa Lignin
journal, October 2009


BEHAVIOR OF EUCALYPTUS GLOBULUS LIGNIN DURING KRAFT PULPING. II. ANALYSIS BY NMR, ESI/MS, AND GPC
journal, January 2002

  • Pinto, Paula C.; Evtuguin, Dmitry V.; Neto, Carlos Pascoal
  • Journal of Wood Chemistry and Technology, Vol. 22, Issue 2-3
  • DOI: 10.1081/WCT-120013356

Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d6/pyridine-d5
journal, January 2010

  • Kim, Hoon; Ralph, John
  • Org. Biomol. Chem., Vol. 8, Issue 3
  • DOI: 10.1039/B916070A

Structural Characterization of Wheat Straw Lignin as Revealed by Analytical Pyrolysis, 2D-NMR, and Reductive Cleavage Methods
journal, December 2011

  • del Río, José C.; Rencoret, Jorge; Prinsen, Pepijn
  • Journal of Agricultural and Food Chemistry, Vol. 60, Issue 23
  • DOI: 10.1021/jf301002n

Nuclear Magnetic Resonance Studies. 4. Analysis of Residual Lignin after Kraft Pulping
journal, August 1998

  • Froass, Peter M.; Ragauskas, Arthur J.; Jiang, Jian-er
  • Industrial & Engineering Chemistry Research, Vol. 37, Issue 8
  • DOI: 10.1021/ie970812c

The effect of isolation method on the chemical structure of residual lignin
journal, October 2003

  • J��skel�inen, A. S.; Sun, Y.; Argyropoulos, D. S.
  • Wood Science and Technology, Vol. 37, Issue 2
  • DOI: 10.1007/s00226-003-0163-y

Oxygen Bleaching of Kraft Pulp 1. Role of Condensed Units
journal, January 1994


Role of Functional Groups in Lignin Inhibition of Enzymatic Hydrolysis of Cellulose to Glucose
journal, March 2008


Works referencing / citing this record:

Promising Techniques for Depolymerization of Lignin into Value-added Chemicals
journal, December 2018


Promising Techniques for Depolymerization of Lignin into Value-added Chemicals
journal, January 2019