Integration of renewable deep eutectic solvents with engineered biomass to achieve a closed-loop biorefinery

Kim, Kwang Ho; Eudes, Aymerick; Jeong, Keunhong; Yoo, Chang Geun; Kim, Chang Soo; Ragauskas, Arthur

doi:10.1073/pnas.1904636116

Title: Integration of renewable deep eutectic solvents with engineered biomass to achieve a closed-loop biorefinery

Journal Article · 23 June 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.1904636116 · OSTI ID:1529169

^[1]; Eudes, Aymerick ^[2]; Jeong, Keunhong ^[3]; Yoo, Chang Geun ^[4]; Kim, Chang Soo ^[5];

^[6]

Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02702, Republic of Korea,, Department of Wood Science, University of British Columbia, Vancouver, BC, V6T 1Z4, Canada,
Feedstocks Division, Joint BioEnergy Institute, Emeryville, CA 94608,, Environmental Genomics and Systems Biology Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720,
Department of Chemistry, Korea Military Academy, Seoul 01805, Republic of Korea,
Department of Paper and Bioprocess Engineering, State University of New York College of Environmental Science and Forestry, Syracuse, NY 13210,
Clean Energy Research Center, Korea Institute of Science and Technology, Seoul 02702, Republic of Korea,
Center for Bioenergy Innovation, University of Tennessee–Oak Ridge National Laboratory Joint Institute for Biological Science, Oak Ridge, TN 37831,, Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831,, Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996,, Center for Renewable Carbon, Department of Forestry, Wildlife, and Fisheries, University of Tennessee, Institute of Agriculture, Knoxville, TN 37996

Significance Deep eutectic solvents (DESs) have gained increasing attention due to their application-friendly properties, including universal solvating capabilities and wide tunability. Additionally, ease of synthesis and broad availability from inexpensive chemical components could render DESs more versatile solvents for biomass pretreatment, as compared with traditional ionic liquids. Because the long-term success of the biorefinery depends on the development of sustainable processes to convert lignocellulosics into biofuels, DESs derived from renewable sources such as lignin are highly desirable. We herein present our innovative process that integrates the use of low-recalcitrant engineered biomass with its pretreatment using lignin-derived DESs. The promising results described by near-theoretical sugar yield demonstrate the effectiveness of the integrated process, opening up opportunities toward a sustainable and circular bioeconomy.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1529169

Alternate ID(s):: OSTI ID: 1545201; OSTI ID: 1561928

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 28 Vol. 116; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (56)

Solubility of Metal Oxides in Deep Eutectic Solvents Based on Choline Chloride Abbott, Andrew P.; Capper, Glen; Davies, David L. Journal of Chemical & Engineering Data, Vol. 51, Issue 4 https://doi.org/10.1021/je060038c	journal	July 2006
Lignin modification improves fermentable sugar yields for biofuel production Chen, Fang; Dixon, Richard A. Nature Biotechnology, Vol. 25, Issue 7, p. 759-761 https://doi.org/10.1038/nbt1316	journal	June 2007
Facilitated delignification in CAD deficient transgenic poplar studied by confocal Raman spectroscopy imaging Segmehl, Jana S.; Keplinger, Tobias; Krasnobaev, Artem Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 206 https://doi.org/10.1016/j.saa.2018.07.080	journal	January 2019
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
Improved saccharification and ethanol yield from field-grown transgenic poplar deficient in cinnamoyl-CoA reductase Van Acker, R.; Leple, J. -C.; Aerts, D. Proceedings of the National Academy of Sciences, Vol. 111, Issue 2 https://doi.org/10.1073/pnas.1321673111	journal	December 2013
Enhancing digestibility and ethanol yield of Populus wood via expression of an engineered monolignol 4-O-methyltransferase Cai, Yuanheng; Zhang, Kewei; Kim, Hoon Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11989	journal	June 2016
Biocompatible Deep Eutectic Solvents Based on Choline Chloride: Characterization and Application to the Extraction of Rutin from Sophora japonica Zhao, Bing-Yi; Xu, Pei; Yang, Fu-Xi ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 11 https://doi.org/10.1021/acssuschemeng.5b00619	journal	October 2015
Impact of lignin polymer backbone esters on ionic liquid pretreatment of poplar Kim, Kwang Ho; Dutta, Tanmoy; Ralph, John Biotechnology for Biofuels, Vol. 10, Issue 1 https://doi.org/10.1186/s13068-017-0784-2	journal	April 2017
Why genetic modification of lignin leads to low-recalcitrance biomass Carmona, Christopher; Langan, Paul; Smith, Jeremy C. Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP05004E	journal	January 2015
Tailor-made trees: engineering lignin for ease of processing and tomorrow’s bioeconomy Mahon, Elizabeth L.; Mansfield, Shawn D. Current Opinion in Biotechnology, Vol. 56 https://doi.org/10.1016/j.copbio.2018.10.014	journal	April 2019
Different Routes for Conifer- and Sinapaldehyde and Higher Saccharification upon Deficiency in the Dehydrogenase CAD1 Van Acker, Rebecca; Déjardin, Annabelle; Desmet, Sandrien Plant Physiology, Vol. 175, Issue 3 https://doi.org/10.1104/pp.17.00834	journal	September 2017
On the molecular origin of the alkali solubility of Gramineae lignins Lapierre, Catherine; Jouin, Dominique; Monties, Bernard Phytochemistry, Vol. 28, Issue 5 https://doi.org/10.1016/S0031-9422(00)97755-0	journal	January 1989
Targeted down-regulation of cytochrome P450 enzymes for forage quality improvement in alfalfa (Medicago sativa L.) Reddy, M. S. S.; Chen, F.; Shadle, G. Proceedings of the National Academy of Sciences, Vol. 102, Issue 46 https://doi.org/10.1073/pnas.0505749102	journal	November 2005
Solubility of CO ₂ in a Choline Chloride + Urea Eutectic Mixture Li, Xiaoyong; Hou, Minqiang; Han, Buxing Journal of Chemical & Engineering Data, Vol. 53, Issue 2 https://doi.org/10.1021/je700638u	journal	February 2008
Brown-midrib maize (bm1) - a mutation affecting the cinnamyl alcohol dehydrogenase gene Halpin, Claire; Holt, Karen; Chojecki, Jan The Plant Journal, Vol. 14, Issue 5 https://doi.org/10.1046/j.1365-313X.1998.00153.x	journal	June 1998
Downregulation of Cinnamyl-Alcohol Dehydrogenase in Switchgrass by RNA Silencing Results in Enhanced Glucose Release after Cellulase Treatment Saathoff, Aaron J.; Sarath, Gautam; Chow, Elaine K. PLoS ONE, Vol. 6, Issue 1 https://doi.org/10.1371/journal.pone.0016416	journal	January 2011
Disrupting the cinnamyl alcohol dehydrogenase 1 gene ( BdCAD1 ) leads to altered lignification and improved saccharification in Brachypodium distachyon Bouvier d'Yvoire, Madeleine; Bouchabke-Coussa, Oumaya; Voorend, Wannes The Plant Journal, Vol. 73, Issue 3 https://doi.org/10.1111/tpj.12053	journal	December 2012
Caffeoyl Shikimate Esterase (CSE) Is an Enzyme in the Lignin Biosynthetic Pathway in Arabidopsis Vanholme, R.; Cesarino, I.; Rataj, K. Science, Vol. 341, Issue 6150 https://doi.org/10.1126/science.1241602	journal	August 2013
Altered Lignin Biosynthesis Improves Cellulosic Bioethanol Production in Transgenic Maize Plants Down-Regulated for Cinnamyl Alcohol Dehydrogenase Fornalé, Silvia; Capellades, Montserrat; Encina, Antonio Molecular Plant, Vol. 5, Issue 4 https://doi.org/10.1093/mp/ssr097	journal	July 2012
A novel deep eutectic solvent-based ionic liquid used as electrolyte for dye-sensitized solar cells Jhong, Huei-Ru; Wong, David Shan-Hill; Wan, Chi-Chao Electrochemistry Communications, Vol. 11, Issue 1 https://doi.org/10.1016/j.elecom.2008.11.001	journal	January 2009
Downregulation of Cinnamyl Alcohol Dehydrogenase (CAD) Leads to Improved Saccharification Efficiency in Switchgrass Fu, Chunxiang; Xiao, Xirong; Xi, Yajun BioEnergy Research, Vol. 4, Issue 3, p. 153-164 https://doi.org/10.1007/s12155-010-9109-z	journal	January 2011
Aqueous ionic liquids and deep eutectic solvents for cellulosic biomass pretreatment and saccharification Xia, Shuqian; Baker, Gary A.; Li, Hao RSC Advances, Vol. 4, Issue 21 https://doi.org/10.1039/c3ra46149a	journal	January 2014
Factors affecting lignin solubility Evstigneev, E. I. Russian Journal of Applied Chemistry, Vol. 84, Issue 6 https://doi.org/10.1134/S1070427211060243	journal	June 2011
NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins Kim, Hoon; Ralph, John; Lu, Fachuang Organic & Biomolecular Chemistry, Vol. 1, Issue 2 https://doi.org/10.1039/b209686b	journal	December 2002
Monolignol Ferulate Transferase Introduces Chemically Labile Linkages into the Lignin Backbone Wilkerson, C. G.; Mansfield, S. D.; Lu, F. Science, Vol. 344, Issue 6179, p. 90-93 https://doi.org/10.1126/science.1250161	journal	April 2014
Deep Eutectic Solvents (DESs) and Their Applications Smith, Emma L.; Abbott, Andrew P.; Ryder, Karl S. Chemical Reviews, Vol. 114, Issue 21 https://doi.org/10.1021/cr300162p	journal	October 2014
Natural deep eutectic solvents for lignocellulosic biomass pretreatment: Recent developments, challenges and novel opportunities Satlewal, Alok; Agrawal, Ruchi; Bhagia, Samarthya Biotechnology Advances, Vol. 36, Issue 8 https://doi.org/10.1016/j.biotechadv.2018.08.009	journal	December 2018
Electrophilicity index as a possible descriptor of biological activity Parthasarathi, R.; Subramanian, V.; Roy, D. R. Bioorganic & Medicinal Chemistry, Vol. 12, Issue 21 https://doi.org/10.1016/j.bmc.2004.08.013	journal	November 2004
Biomass pretreatment using deep eutectic solvents from lignin derived phenols Kim, Kwang Ho; Dutta, Tanmoy; Sun, Jian Green Chemistry, Vol. 20, Issue 4 https://doi.org/10.1039/C7GC03029K	journal	January 2018
Loss of function of cinnamyl alcohol dehydrogenase 1 leads to unconventional lignin and a temperature-sensitive growth defect in Medicago truncatula Zhao, Q.; Tobimatsu, Y.; Zhou, R. Proceedings of the National Academy of Sciences, Vol. 110, Issue 33 https://doi.org/10.1073/pnas.1312234110	journal	July 2013
Evaluation of Brown Midrib Sorghum Mutants as a Potential Biomass Feedstock for 2,3-Butanediol Biosynthesis Guragain, Yadhu N.; Srinivasa Rao, P.; Vara Prasad, Pv Applied Biochemistry and Biotechnology, Vol. 183, Issue 3 https://doi.org/10.1007/s12010-017-2486-4	journal	April 2017
Elucidating Structural Characteristics of Biomass using Solution-State 2 D NMR with a Mixture of Deuterated Dimethylsulfoxide and Hexamethylphosphoramide Yoo, Chang Geun; Pu, Yunqiao; Li, Mi ChemSusChem, Vol. 9, Issue 10 https://doi.org/10.1002/cssc.201600135	journal	April 2016
Biomass pretreatment: Fundamentals toward application Agbor, Valery B.; Cicek, Nazim; Sparling, Richard Biotechnology Advances, Vol. 29, Issue 6 https://doi.org/10.1016/j.biotechadv.2011.05.005	journal	November 2011
Efficient biomass pretreatment using ionic liquids derived from lignin and hemicellulose Socha, A. M.; Parthasarathi, R.; Shi, J. Proceedings of the National Academy of Sciences, Vol. 111, Issue 35 https://doi.org/10.1073/pnas.1405685111	journal	August 2014
Natural deep eutectic solvent mediated pretreatment of rice straw: bioanalytical characterization of lignin extract and enzymatic hydrolysis of pretreated biomass residue Kumar, Adepu K.; Parikh, Bhumika S.; Pravakar, Mohanty Environmental Science and Pollution Research, Vol. 23, Issue 10 https://doi.org/10.1007/s11356-015-4780-4	journal	June 2015
Field and pulping performances of transgenic trees with altered lignification Pilate, Gilles; Guiney, Emma; Holt, Karen Nature Biotechnology, Vol. 20, Issue 6 https://doi.org/10.1038/nbt0602-607	journal	June 2002
Deep Eutectic Solvents: Physicochemical Properties and Gas Separation Applications García, Gregorio; Aparicio, Santiago; Ullah, Ruh Energy & Fuels, Vol. 29, Issue 4 https://doi.org/10.1021/ef5028873	journal	March 2015
Unique low-molecular-weight lignin with high purity extracted from wood by deep eutectic solvents (DES): a source of lignin for valorization Alvarez-Vasco, Carlos; Ma, Ruoshui; Quintero, Melissa Green Chemistry, Vol. 18, Issue 19 https://doi.org/10.1039/C6GC01007E	journal	January 2016
A Nonsense Mutation in a Cinnamyl Alcohol Dehydrogenase Gene Is Responsible for the Sorghum brown midrib6 Phenotype Sattler, Scott E.; Saathoff, Aaron J.; Haas, Eric J. Plant Physiology, Vol. 150, Issue 2 https://doi.org/10.1104/pp.109.136408	journal	April 2009
Signatures of cinnamyl alcohol dehydrogenase deficiency in poplar lignins Lapierre, Catherine; Pilate, Gilles; Pollet, Brigitte Phytochemistry, Vol. 65, Issue 3 https://doi.org/10.1016/j.phytochem.2003.11.007	journal	February 2004
Deep eutectic solvent pretreatment and subsequent saccharification of corncob Procentese, Alessandra; Johnson, Erin; Orr, Valerie Bioresource Technology, Vol. 192 https://doi.org/10.1016/j.biortech.2015.05.053	journal	September 2015
Breeding silage maize with brown-midrib genes. Feeding value and biochemical characteristics Barrière, Y.; Argillier, O.; Chabbert, B. Agronomie, Vol. 14, Issue 1 https://doi.org/10.1051/agro:19940102	journal	January 1994
The lignin present in steam pretreated softwood binds enzymes and limits cellulose accessibility Kumar, Linoj; Arantes, Valdeir; Chandra, Richard Bioresource Technology, Vol. 103, Issue 1 https://doi.org/10.1016/j.biortech.2011.09.091	journal	January 2012
Electrophilicity Index Parr, Robert G.; Szentpály, László v.; Liu, Shubin Journal of the American Chemical Society, Vol. 121, Issue 9 https://doi.org/10.1021/ja983494x	journal	March 1999
Electrophilicity Index Chattaraj, Pratim Kumar; Sarkar, Utpal; Roy, Debesh Ranjan Chemical Reviews, Vol. 106, Issue 6 https://doi.org/10.1021/cr040109f	journal	June 2006
Forage Yield and Economic Losses Associated with the Brown-Midrib Trait in Sudangrass Casler, M. D.; Pedersen, J. F.; Undersander, D. J. Crop Science, Vol. 43, Issue 3 https://doi.org/10.2135/cropsci2003.7820	journal	January 2003
Efficacy of Singular and Stacked brown midrib 6 and 12 in the Modification of Lignocellulose and Grain Chemistry Sattler, Scott E.; Funnell-Harris, Deanna L.; Pedersen, Jeffrey F. Journal of Agricultural and Food Chemistry, Vol. 58, Issue 6 https://doi.org/10.1021/jf903784j	journal	March 2010
Impact of engineered lignin composition on biomass recalcitrance and ionic liquid pretreatment efficiency Shi, Jian; Pattathil, Sivakumar; Parthasarathi, Ramakrishnan Green Chemistry, Vol. 18, Issue 18 https://doi.org/10.1039/C6GC01193D	journal	January 2016
Plant cell walls are enfeebled when attempting to preserve native lignin configuration with poly-p-hydroxycinnamaldehydes: Evolutionary implications Jourdes, Michaël; Cardenas, Claudia L.; Laskar, Dhrubojyoti D. Phytochemistry, Vol. 68, Issue 14 https://doi.org/10.1016/j.phytochem.2007.03.044	journal	July 2007
Improving Saccharification Efficiency of Alfalfa Stems Through Modification of the Terminal Stages of Monolignol Biosynthesis Jackson, Lisa A.; Shadle, Gail L.; Zhou, Rui BioEnergy Research, Vol. 1, Issue 3-4 https://doi.org/10.1007/s12155-008-9020-z	journal	September 2008
Facile pretreatment of lignocellulosic biomass using deep eutectic solvents Zhang, Cheng-Wu; Xia, Shu-Qian; Ma, Pei-Sheng Bioresource Technology, Vol. 219 https://doi.org/10.1016/j.biortech.2016.07.026	journal	November 2016
Novel solvent properties of choline chloride/urea mixturesElectronic supplementary information (ESI) available: spectroscopic data. See http://www.rsc.org/suppdata/cc/b2/b210714g/ Abbott, Andrew P.; Capper, Glen; Davies, David L. Chemical Communications, Issue 1 https://doi.org/10.1039/b210714g	journal	November 2002
Artificial miRNA-mediated down-regulation of two monolignoid biosynthetic genes (C3H and F5H) cause reduction in lignin content in jute Shafrin, Farhana; Das, Sudhanshu Sekhar; Sanan-Mishra, Neeti Plant Molecular Biology, Vol. 89, Issue 4-5 https://doi.org/10.1007/s11103-015-0385-z	journal	October 2015
CINNAMYL ALCOHOL DEHYDROGENASE-C and -D Are the Primary Genes Involved in Lignin Biosynthesis in the Floral Stem of Arabidopsis Sibout, Richard; Eudes, Aymerick; Mouille, Gregory The Plant Cell, Vol. 17, Issue 7 https://doi.org/10.1105/tpc.105.030767	journal	June 2005
Enhancing cellulose accessibility of corn stover by deep eutectic solvent pretreatment for butanol fermentation Xu, Guo-Chao; Ding, Ji-Cai; Han, Rui-Zhi Bioresource Technology, Vol. 203 https://doi.org/10.1016/j.biortech.2015.11.002	journal	March 2016
Enhancing alfalfa conversion efficiencies for sugar recovery and ethanol production by altering lignin composition Dien, Bruce S.; Miller, David J.; Hector, Ronald E. Bioresource Technology, Vol. 102, Issue 11, p. 6479-6486 https://doi.org/10.1016/j.biortech.2011.03.022	journal	June 2011

Similar Records

Engineered Sorghum Bagasse Enables a Sustainable Biorefinery with p-Hydroxybenzoic Acid-Based Deep Eutectic Solvent

Journal Article · 2021 · ChemSusChem · OSTI ID:1841469

Wang, Yunxuan; Meng, Xianzhi; Tian, Yang; +8 more

Utilization of guaiacol-based deep eutectic solvent for achieving a sustainable biorefinery

Journal Article · 2022 · Bioresource Technology · OSTI ID:1886483

Huang, Chen; Cheng, Jinyuan; Zhan, Yunni; +8 more

Applications of biomass-derived solvents in biomass pretreatment – Strategies, challenges, and prospects

Journal Article · 2022 · Bioresource Technology · OSTI ID:1906566

Meng, Xianzhi; Wang, Yunxuan; Conte, Austin J.; +7 more

Title: Integration of renewable deep eutectic solvents with engineered biomass to achieve a closed-loop biorefinery

Citation Formats

References (56)

Similar Records

Related Subjects