Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments

Luna Liang; Yun Yan Wang; Samarthya Bhagia; Vaidyanathan Sethuraman; Zhi Yang; Xianzhi Meng; Nathan Bryant; Loukas Petridis; Jeremy C. Smith; Sai Venkatesh Pingali; Nidia C. Gallego; Yunqiao Pu; Barbara R. Evans; Hugh M. O'neill; Brian H. Davison; Arthur J. Ragauskas

doi:10.1021/acssuschemeng.2c00948

Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments

Luna Liang, Yun Yan Wang, Samarthya Bhagia, Vaidyanathan Sethuraman, Zhi Yang, Xianzhi Meng, Nathan Bryant, Loukas Petridis, Jeremy C. Smith, Sai Venkatesh Pingali, Nidia C. Gallego, Yunqiao Pu, Barbara R. Evans, Hugh M. O'neill, Brian H. Davison, Arthur J. Ragauskas

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Abstract

The recalcitrance of lignocellulosic biomass is a challenge in biological-based biorefinery systems due to the complex physicochemical structure of plant cell walls. Pretreatment and genetic modification are two approaches in biomass conversion that have succeeded in modifying the structure of lignocellulose to enable better enzymatic deconstruction. However, the structural differences among pretreatment-solubilized lignin isolated from switchgrass genotypes have not been extensively investigated. Here, three organosolv pretreatment systems─ethanol (EtOH), tetrahydrofuran (THF), and γ-valerolactone (GVL)─were used on wild-type (WT) and two transgenic switchgrasses. All organosolv pretreatments caused a significant reduction in the molecular mass of lignins; particularly, up to ∼90% decrease was observed in EtOH-pretreated lignin compared to untreated lignin. The WT EtOH lignin also presented the smallest particle size among all WT lignins. THF pretreated transgenic lignins showed a higher molecular mass, β-O-4 linkages, and aliphatic hydroxyl content compared to EtOH and GVL pretreated lignin. The number of hydrogen bonds between lignin and the organic solvents calculated from the molecular dynamics simulations followed the same trend as the experimentally determined reduction in lignin molecular mass. The results revealed the structural changes of solubilized lignin isolated from wild-type and transgenic switchgrass after different organosolv pretreatments.

Original language	English
Pages (from-to)	9041-9052
Number of pages	12
Journal	ACS Sustainable Chemistry and Engineering
Volume	10
Issue number	28
DOIs	https://doi.org/10.1021/acssuschemeng.2c00948
State	Published - Jul 18 2022

Funding

We are grateful for funding from the Genomic Science Program (contract FWP ERKP752) at Oak Ridge National Laboratory. SAXS measurements were performed at the LiX beamline of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. LiX beamline is supported under the Center for BioMolecular Structure (CBMS), which is primarily supported by the National Institutes of Health and National Institute of General Medical Sciences (NIGMS) through a Center Core P30 Grant (P30GM133893) and by the DOE Office of Biological and Environmental Research (KP1605010). Z.Y., S.V.P., and H.O.N. acknowledge Dr. Marcella Berg for accompanying Z.Y. to NSLS-II and assisting with these experiments and also Dr. Shishir Chodankar and Dr. Lin Yang, the LiX beamline staff, for all their patience, guidance, and facilitation of a successful experiment. This research used the Oak Ridge Leadership Computing Facility resources at the Oak Ridge National Laboratory under an INCITE award, which is supported by the Office of Science of the U.S. Department of Energy. Oak Ridge National Laboratory is managed by UT-Battelle, LLC under Contract DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government and the publisher, by accepting the article for publication, acknowledge that the United States government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this article or allow others to do so for United States government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ). The views and opinions of the authors expressed herein do not necessarily state or reflect those of the United States government or any agency thereof. Neither the United States government nor any agency thereof or any of their employees make any warranty, expressed or implied, or assume any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed or represent that its use would not infringe privately owned rights.

Keywords

lignin structure
organosolv pretreatment
small-angle X-ray scattering
switchgrass
transgenic switchgrass

Access to Document

10.1021/acssuschemeng.2c00948

Cite this

Liang, L., Wang, Y. Y., Bhagia, S., Sethuraman, V., Yang, Z., Meng, X., Bryant, N., Petridis, L., Smith, J. C., Pingali, S. V., Gallego, N. C., Pu, Y., Evans, B. R., O'neill, H. M., Davison, B. H., & Ragauskas, A. J. (2022). Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments. ACS Sustainable Chemistry and Engineering, 10(28), 9041-9052. https://doi.org/10.1021/acssuschemeng.2c00948

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title = "Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments",

abstract = "The recalcitrance of lignocellulosic biomass is a challenge in biological-based biorefinery systems due to the complex physicochemical structure of plant cell walls. Pretreatment and genetic modification are two approaches in biomass conversion that have succeeded in modifying the structure of lignocellulose to enable better enzymatic deconstruction. However, the structural differences among pretreatment-solubilized lignin isolated from switchgrass genotypes have not been extensively investigated. Here, three organosolv pretreatment systems─ethanol (EtOH), tetrahydrofuran (THF), and γ-valerolactone (GVL)─were used on wild-type (WT) and two transgenic switchgrasses. All organosolv pretreatments caused a significant reduction in the molecular mass of lignins; particularly, up to ∼90% decrease was observed in EtOH-pretreated lignin compared to untreated lignin. The WT EtOH lignin also presented the smallest particle size among all WT lignins. THF pretreated transgenic lignins showed a higher molecular mass, β-O-4 linkages, and aliphatic hydroxyl content compared to EtOH and GVL pretreated lignin. The number of hydrogen bonds between lignin and the organic solvents calculated from the molecular dynamics simulations followed the same trend as the experimentally determined reduction in lignin molecular mass. The results revealed the structural changes of solubilized lignin isolated from wild-type and transgenic switchgrass after different organosolv pretreatments.",

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author = "Luna Liang and Wang, {Yun Yan} and Samarthya Bhagia and Vaidyanathan Sethuraman and Zhi Yang and Xianzhi Meng and Nathan Bryant and Loukas Petridis and Smith, {Jeremy C.} and Pingali, {Sai Venkatesh} and Gallego, {Nidia C.} and Yunqiao Pu and Evans, {Barbara R.} and O'neill, {Hugh M.} and Davison, {Brian H.} and Ragauskas, {Arthur J.}",

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Liang, L, Wang, YY, Bhagia, S, Sethuraman, V, Yang, Z, Meng, X, Bryant, N, Petridis, L, Smith, JC, Pingali, SV , Gallego, NC , Pu, Y , Evans, BR , O'neill, HM , Davison, BH & Ragauskas, AJ 2022, 'Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments', ACS Sustainable Chemistry and Engineering, vol. 10, no. 28, pp. 9041-9052. https://doi.org/10.1021/acssuschemeng.2c00948

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AU - Bhagia, Samarthya

AU - Sethuraman, Vaidyanathan

AU - Yang, Zhi

AU - Meng, Xianzhi

AU - Bryant, Nathan

AU - Petridis, Loukas

AU - Smith, Jeremy C.

AU - Pingali, Sai Venkatesh

AU - Gallego, Nidia C.

AU - Pu, Yunqiao

AU - Evans, Barbara R.

AU - O'neill, Hugh M.

AU - Davison, Brian H.

AU - Ragauskas, Arthur J.

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Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments

Abstract

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Keywords

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Simulation dataset for "Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and Î³-Valerolactone Pretreatments"

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Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and γ-Valerolactone Pretreatments

Abstract

Funding

Keywords

Access to Document

Other files and links

Fingerprint

Datasets

Simulation dataset for "Chemical and Morphological Structure of Transgenic Switchgrass Organosolv Lignin Extracted by Ethanol, Tetrahydrofuran, and Î³-Valerolactone Pretreatments"

Cite this