Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

Sun, Qining; Pu, Yunqiao; Meng, Xianzhi; Wells, Tyrone; Ragauskas, Arthur J.

doi:10.1021/acssuschemeng.5b00426

Title: Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

Journal Article · Thu Aug 27 00:00:00 EDT 2015 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.5b00426· OSTI ID:1237597

Sun, Qining ^[1]; Pu, Yunqiao ^[2]; Meng, Xianzhi ^[1]; Wells, Tyrone ^[1]; Ragauskas, Arthur J. ^[3]

Georgia Inst. of Technology, Atlanta, GA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

A key step in conversion of cellulosic biomass into sustainable fuels and chemicals is thermochemical pretreatment to reduce plant cell wall recalcitrance. Obtaining an improved understanding of the fundamental chemistry of lignin, the most recalcitrant component of biomass, during pretreatment is critical to the continued development of renewable biofuel production. To examine the intrinsic chemistry of lignin during dilute acid pretreatment (DAP), lignin was isolated from poplar and switchgrass using a cellulolytic enzyme system and then treated under DAP conditions. These results highlight that lignin is subjected to depolymerization reactions within the first 2 min of dilute acid pretreatment and these changes are accompanied by increased generation of aliphatic and phenolic hydroxyl groups of lignin. This is followed by a competing set of depolymerization and repolymerization reactions that lead to a decrease in the content of guaiacyl lignin units and an increase in condensed lignin units as the reaction residence time is extended beyond 5 min. Finally, we showed that a detailed comparison of changes in functional groups and molecular weights of cellulolytic enzyme lignins with different structural parameters, related to the recalcitrant properties of lignin, could be successfully altered during DAP conditions.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1237597

Journal Information:: ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 9; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 32 works

Citation information provided by
Web of Science

References (28)

The Path Forward for Biofuels and Biomaterials Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H. Science, Vol. 311, Issue 5760, p. 484-489 https://doi.org/10.1126/science.1114736	journal	January 2006
Application of quantitative 31P NMR in biomass lignin and biofuel precursors characterization Pu, Yunqiao; Cao, Shilin; Ragauskas, Arthur J. Energy & Environmental Science, Vol. 4, Issue 9 https://doi.org/10.1039/c1ee01201k	journal	January 2011
Effect of Lignin Chemistry on the Enzymatic Hydrolysis of Woody Biomass Yu, Zhiying; Gwak, Ki-Seob; Treasure, Trevor ChemSusChem, Vol. 7, Issue 7 https://doi.org/10.1002/cssc.201400042	journal	June 2014
Assessing the molecular structure basis for biomass recalcitrance during dilute acid and hydrothermal pretreatments Pu, Yunqiao; Hu, Fan; Huang, Fang Biotechnology for Biofuels, Vol. 6, Issue 1 https://doi.org/10.1186/1754-6834-6-15	journal	January 2013
Investigating plant cell wall components that affect biomass recalcitrance in poplar and switchgrass DeMartini, Jaclyn D.; Pattathil, Sivakumar; Miller, Jeffrey S. Energy & Environmental Science, Vol. 6, Issue 3 https://doi.org/10.1039/c3ee23801f	journal	January 2013
Lignin plays a negative role in the biochemical process for producing lignocellulosic biofuels Zeng, Yining; Zhao, Shuai; Yang, Shihui Current Opinion in Biotechnology, Vol. 27 https://doi.org/10.1016/j.copbio.2013.09.008	journal	June 2014
Lignin content in natural Populus variants affects sugar release Studer, M. H.; DeMartini, J. D.; Davis, M. F. Proceedings of the National Academy of Sciences, Vol. 108, Issue 15, p. 6300-6305 https://doi.org/10.1073/pnas.1009252108	journal	March 2011
Lignin Valorization: Improving Lignin Processing in the Biorefinery Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J. Science, Vol. 344, Issue 6185, p. 1246843-1246843 https://doi.org/10.1126/science.1246843	journal	May 2014
Comparative sugar recovery and fermentation data following pretreatment of poplar wood by leading technologies Wyman, Charles E.; Dale, Bruce E.; Elander, Richard T. Biotechnology Progress, Vol. 25, Issue 2 https://doi.org/10.1002/btpr.142	journal	March 2009
Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment Donohoe, Bryon S.; Decker, Stephen R.; Tucker, Melvin P. Biotechnology and Bioengineering, Vol. 101, Issue 5 https://doi.org/10.1002/bit.21959	journal	December 2008
Investigation of lignin deposition on cellulose during hydrothermal pretreatment, its effect on cellulose hydrolysis, and underlying mechanisms: Investigation of Lignin Deposition on Cellulose Li, Hongjia; Pu, Yunqiao; Kumar, Rajeev Biotechnology and Bioengineering, Vol. 111, Issue 3 https://doi.org/10.1002/bit.25108	journal	October 2013
Three-stage enzymatic hydrolysis of steam-exploded corn stover at high substrate concentration Yang, Jing; Zhang, Xiaoping; Yong, Qiang Bioresource Technology, Vol. 102, Issue 7 https://doi.org/10.1016/j.biortech.2010.12.047	journal	April 2011
Investigation of the fate of poplar lignin during autohydrolysis pretreatment to understand the biomass recalcitrance Samuel, Reichel; Cao, Shilin; Das, Birinchi K. RSC Advances, Vol. 3, Issue 16 https://doi.org/10.1039/c3ra40578h	journal	January 2013
Structural Characterization and Comparison of Switchgrass Ball-milled Lignin Before and After Dilute Acid Pretreatment Samuel, Reichel; Pu, Yunqiao; Raman, Babu Applied Biochemistry and Biotechnology, Vol. 162, Issue 1 https://doi.org/10.1007/s12010-009-8749-y	journal	August 2009
Chemical transformations of Populus trichocarpa during dilute acid pretreatment Cao, Shilin; Pu, Yunqiao; Studer, Michael RSC Advances, Vol. 2, Issue 29 https://doi.org/10.1039/c2ra22045h	journal	January 2012
Hydrothermal Pretreatment of Switchgrass Hu, Zhoujian; Ragauskas, Arthur J. Industrial & Engineering Chemistry Research, Vol. 50, Issue 8 https://doi.org/10.1021/ie101886d	journal	April 2011
Characterisation of lignin-carbohydrate complexes (LCCs) of spruce wood (Picea abies L.) isolated with two methods Lawoko, Martin; Henriksson, Gunnar; Gellerstedt, Göran Holzforschung, Vol. 60, Issue 2 https://doi.org/10.1515/HF.2006.025	journal	March 2006
Elucidation of the structure of cellulolytic enzyme lignin Hu, Zhoujian; Yeh, Ting-Feng; Chang, Hou-min Holzforschung, Vol. 60, Issue 4 https://doi.org/10.1515/HF.2006.061	journal	July 2006
Pretreatment with laccase and a phenolic mediator degrades lignin and enhances saccharification of Eucalyptus feedstock Rico, Alejandro; Rencoret, Jorge; del Río, José C. Biotechnology for Biofuels, Vol. 7, Issue 1 https://doi.org/10.1186/1754-6834-7-6	journal	January 2014
Comparison of changes in cellulose ultrastructure during different pretreatments of poplar Sun, Qining; Foston, Marcus; Sawada, Daisuke Cellulose, Vol. 21, Issue 4 https://doi.org/10.1007/s10570-014-0303-6	journal	May 2014
Characterization of CO ₂ precipitated Kraft lignin to promote its utilization Nagy, Máté; Kosa, Matyas; Theliander, Hans Green Chem., Vol. 12, Issue 1 https://doi.org/10.1039/B913602A	journal	January 2010
Biomass Characterization of Buddleja davidii: A Potential Feedstock for Biofuel Production Hallac, Bassem B.; Sannigrahi, Poulomi; Pu, Yunqiao Journal of Agricultural and Food Chemistry, Vol. 57, Issue 4 https://doi.org/10.1021/jf8030277	journal	February 2009
Pseudo-lignin and pretreatment chemistry Sannigrahi, Poulomi; Kim, Dong Ho; Jung, Seokwon Energy Environ. Sci., Vol. 4, Issue 4 https://doi.org/10.1039/C0EE00378F	journal	January 2011
The fate of lignin during hydrothermal pretreatment Trajano, Heather L.; Engle, Nancy L.; Foston, Marcus Biotechnology for Biofuels, Vol. 6, Issue 1 https://doi.org/10.1186/1754-6834-6-110	journal	January 2013
Structural changes in switchgrass lignin and hemicelluloses during pretreatments by NMR analysis Samuel, Reichel; Foston, Marcus; Jiang, Nan Polymer Degradation and Stability, Vol. 96, Issue 11 https://doi.org/10.1016/j.polymdegradstab.2011.08.015	journal	November 2011
Enhancing the enzymatic hydrolysis of lignocellulosic biomass by increasing the carboxylic acid content of the associated lignin Nakagame, Seiji; Chandra, Richard P.; Kadla, John F. Biotechnology and Bioengineering, Vol. 108, Issue 3 https://doi.org/10.1002/bit.22981	journal	November 2010
Lignin depolymerization/repolymerization and its critical role for delignification of aspen wood by steam explosion Li, Jiebing; Henriksson, Gunnar; Gellerstedt, Göran Bioresource Technology, Vol. 98, Issue 16 https://doi.org/10.1016/j.biortech.2006.10.018	journal	November 2007
Structural changes of corn stover lignin during acid pretreatment Moxley, Geoffrey; Gaspar, Armindo Ribeiro; Higgins, Don Journal of Industrial Microbiology & Biotechnology, Vol. 39, Issue 9 https://doi.org/10.1007/s10295-012-1131-z	journal	April 2012

Cited By (8)

Diol pretreatment to fractionate a reactive lignin in lignocellulosic biomass biorefineries Dong, Chengyu; Meng, Xianzhi; Yeung, Chi Shun Green Chemistry, Vol. 21, Issue 10 https://doi.org/10.1039/c9gc00596j	journal	January 2019
Understanding the structural characteristics of water-soluble phenolic compounds from four pretreatments of corn stover and their inhibitory effects on enzymatic hydrolysis and fermentation Chen, Xiangxue; Zhai, Rui; Li, Ying Biotechnology for Biofuels, Vol. 13, Issue 1 https://doi.org/10.1186/s13068-020-01686-z	journal	March 2020
Ethanol: A Promising Green Solvent for the Deconstruction of Lignocellulose Tekin, Kubilay; Hao, Naijia; Karagoz, Selhan ChemSusChem, Vol. 11, Issue 20 https://doi.org/10.1002/cssc.201801291	journal	September 2018
Preparation and Properties of Jute Fiber Long-Chain Fatty Acid Esters in Supercritical Carbon Dioxide Li, Chong; Jiang, Yueping; Huang, Baoshan Materials, Vol. 12, Issue 9 https://doi.org/10.3390/ma12091499	journal	May 2019
An economically viable ionic liquid for the fractionation of lignocellulosic biomass Brandt-Talbot, Agnieszka; Gschwend, Florence J. V.; Fennell, Paul S. Green Chemistry, Vol. 19, Issue 13 https://doi.org/10.1039/c7gc00705a	journal	January 2017
Rapid pretreatment of Miscanthus using the low-cost ionic liquid triethylammonium hydrogen sulfate at elevated temperatures Gschwend, Florence J. V.; Malaret, Francisco; Shinde, Somnath Green Chemistry, Vol. 20, Issue 15 https://doi.org/10.1039/c8gc00837j	journal	January 2018
An In-Depth Understanding of Biomass Recalcitrance Using Natural Poplar Variants as the Feedstock Meng, Xianzhi; Pu, Yunqiao; Yoo, Chang Geun ChemSusChem, Vol. 10, Issue 1 https://doi.org/10.1002/cssc.201601303	journal	December 2016
Impact of hydration and temperature history on the structure and dynamics of lignin Vural, Derya; Gainaru, Catalin; O'Neill, Hugh Green Chemistry, Vol. 20, Issue 7 https://doi.org/10.1039/c7gc03796a	journal	January 2018

Similar Records

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

Journal Article · Tue Dec 01 00:00:00 EST 2015 · Biotechnology for Biofuels · OSTI ID:1237597

Zhang, Libing; Yan, Lishi; Wang, Zheming; +4 more

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

Journal Article · Tue Oct 14 00:00:00 EDT 2014 · Biotechnology for Biofuels · OSTI ID:1237597

Sun, Qining; Foston, Marcus; Meng, Xianzhi; +8 more

Understanding Multiscale Structural Changes During Dilute Acid Pretreatment of Switchgrass and Poplar

Journal Article · Mon Dec 05 00:00:00 EST 2016 · ACS Sustainable Chemistry & Engineering · OSTI ID:1237597

Pingali, Sai Venkatesh; Urban, Volker S.; Heller, William T.; +10 more

Related Subjects

09 BIOMASS FUELS
poplar
switchgrass
dilute acid pretreatment
cellulolytic enzyme lignin
reaction mechanism

Title: Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

Citation Formats

References (28)

Cited By (8)

Similar Records

Related Subjects