Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces

Sai Venkatesh Pingali; Micholas Dean Smith; Shih Hsien Liu; Takat B. Rawal; Yunqiao Pu; Riddhi Shah; Barbara R. Evans; Volker S. Urban; Brian H. Davison; Charles M. Cai; Arthur J. Ragauskas; Hugh M. O'Neill; Jeremy C. Smith; Loukas Petridis

doi:10.1073/pnas.1922883117

Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces

Sai Venkatesh Pingali, Micholas Dean Smith, Shih Hsien Liu, Takat B. Rawal, Yunqiao Pu, Riddhi Shah, Barbara R. Evans, Volker S. Urban, Brian H. Davison, Charles M. Cai, Arthur J. Ragauskas, Hugh M. O'Neill, Jeremy C. Smith, Loukas Petridis

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

A particularly promising approach to deconstructing and fractionating lignocellulosic biomass to produce green renewable fuels and high-value chemicals pretreats the biomass with organic solvents in aqueous solution. Here, neutron scattering and molecular-dynamics simulations reveal the temperature-dependent morphological changes in poplar wood biomass during tetrahydrofuran (THF):water pretreatment and provide a mechanism by which the solvent components drive efficient biomass breakdown. Whereas lignin dissociates over a wide temperature range (>25 °C) cellulose disruption occurs only above 150 °C. Neutron scattering with contrast variation provides direct evidence for the formation of THF-rich nanoclusters (R_g ∼ 0.5 nm) on the nonpolar cellulose surfaces and on hydrophobic lignin, and equivalent water-rich nanoclusters on polar cellulose surfaces. The disassembly of the amphiphilic biomass is thus enabled through the local demixing of highly functional cosolvents, THF and water, which preferentially solvate specific biomass surfaces so as to match the local solute polarity. A multiscale description of the efficiency of THF:water pretreatment is provided: matching polarity at the atomic scale prevents lignin aggregation and disrupts cellulose, leading to improvements in deconstruction at the macroscopic scale.

Original language	English
Pages (from-to)	16776-16781
Number of pages	6
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	117
Issue number	29
DOIs	https://doi.org/10.1073/pnas.1922883117
State	Published - Jul 21 2020

Funding

ACKNOWLEDGMENTS. This research was supported by the Genomic Science Program, Office of Biological and Environmental Research (OBER), Office of Science, US Department of Energy (DOE), under Contract FWP ERKP752. C.M.C. was supported by the OBER through the Center for Bioenergy Innovation, managed by Oak Ridge National Laboratory. This research used resources of two DOE Office of Science User Facilities: The HFIR at Oak Ridge National Laboratory and the Oak Ridge Leadership Computing Facility. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for the US DOE under Contract DE-AC05-00OR22725. This manuscript has been authored by UT-Battelle, LLC under Contract DE-AC05-00OR22725 with the US DOE. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe-public-access-plan). This research was supported by the Genomic Science Program, Office of Biological and Environmental Research (OBER), Office of Science, US Department of Energy (DOE), under Contract FWP ERKP752. C.M.C. was supported by the OBER through the Center for Bioenergy Innovation, managed by Oak Ridge National Laboratory. This research used resources of two DOE Office of Science User Facilities: The HFIR at Oak Ridge National Laboratory and the Oak Ridge Leadership Computing Facility. Oak Ridge National Laboratory is managed by UT-Battelle, LLC, for the US DOE under Contract DE-AC05-00OR22725. This manuscript has been authored by UT-Battelle, LLC under Contract DE-AC05-00OR22725 with the US DOE. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, worldwide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The DOE will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (https://energy.gov/downloads/doe-public-access-plan).

Keywords

Biomass
Pretreatment
Solvents

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1073/pnas.1922883117

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Pingali, S. V., Smith, M. D., Liu, S. H., Rawal, T. B., Pu, Y., Shah, R., Evans, B. R., Urban, V. S., Davison, B. H., Cai, C. M., Ragauskas, A. J., O'Neill, H. M., Smith, J. C., & Petridis, L. (2020). Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces. Proceedings of the National Academy of Sciences of the United States of America, 117(29), 16776-16781. https://doi.org/10.1073/pnas.1922883117

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abstract = "A particularly promising approach to deconstructing and fractionating lignocellulosic biomass to produce green renewable fuels and high-value chemicals pretreats the biomass with organic solvents in aqueous solution. Here, neutron scattering and molecular-dynamics simulations reveal the temperature-dependent morphological changes in poplar wood biomass during tetrahydrofuran (THF):water pretreatment and provide a mechanism by which the solvent components drive efficient biomass breakdown. Whereas lignin dissociates over a wide temperature range (>25 °C) cellulose disruption occurs only above 150 °C. Neutron scattering with contrast variation provides direct evidence for the formation of THF-rich nanoclusters (Rg ∼ 0.5 nm) on the nonpolar cellulose surfaces and on hydrophobic lignin, and equivalent water-rich nanoclusters on polar cellulose surfaces. The disassembly of the amphiphilic biomass is thus enabled through the local demixing of highly functional cosolvents, THF and water, which preferentially solvate specific biomass surfaces so as to match the local solute polarity. A multiscale description of the efficiency of THF:water pretreatment is provided: matching polarity at the atomic scale prevents lignin aggregation and disrupts cellulose, leading to improvements in deconstruction at the macroscopic scale.",

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Pingali, SV, Smith, MD, Liu, SH, Rawal, TB, Pu, Y, Shah, R, Evans, BR , Urban, VS , Davison, BH, Cai, CM, Ragauskas, AJ, O'Neill, HM, Smith, JC & Petridis, L 2020, 'Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces', Proceedings of the National Academy of Sciences of the United States of America, vol. 117, no. 29, pp. 16776-16781. https://doi.org/10.1073/pnas.1922883117

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T1 - Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces

AU - Pingali, Sai Venkatesh

AU - Smith, Micholas Dean

AU - Liu, Shih Hsien

AU - Rawal, Takat B.

AU - Pu, Yunqiao

AU - Shah, Riddhi

AU - Evans, Barbara R.

AU - Urban, Volker S.

AU - Davison, Brian H.

AU - Cai, Charles M.

AU - Ragauskas, Arthur J.

AU - O'Neill, Hugh M.

AU - Smith, Jeremy C.

AU - Petridis, Loukas

PY - 2020/7/21

Y1 - 2020/7/21

N2 - A particularly promising approach to deconstructing and fractionating lignocellulosic biomass to produce green renewable fuels and high-value chemicals pretreats the biomass with organic solvents in aqueous solution. Here, neutron scattering and molecular-dynamics simulations reveal the temperature-dependent morphological changes in poplar wood biomass during tetrahydrofuran (THF):water pretreatment and provide a mechanism by which the solvent components drive efficient biomass breakdown. Whereas lignin dissociates over a wide temperature range (>25 °C) cellulose disruption occurs only above 150 °C. Neutron scattering with contrast variation provides direct evidence for the formation of THF-rich nanoclusters (Rg ∼ 0.5 nm) on the nonpolar cellulose surfaces and on hydrophobic lignin, and equivalent water-rich nanoclusters on polar cellulose surfaces. The disassembly of the amphiphilic biomass is thus enabled through the local demixing of highly functional cosolvents, THF and water, which preferentially solvate specific biomass surfaces so as to match the local solute polarity. A multiscale description of the efficiency of THF:water pretreatment is provided: matching polarity at the atomic scale prevents lignin aggregation and disrupts cellulose, leading to improvements in deconstruction at the macroscopic scale.

AB - A particularly promising approach to deconstructing and fractionating lignocellulosic biomass to produce green renewable fuels and high-value chemicals pretreats the biomass with organic solvents in aqueous solution. Here, neutron scattering and molecular-dynamics simulations reveal the temperature-dependent morphological changes in poplar wood biomass during tetrahydrofuran (THF):water pretreatment and provide a mechanism by which the solvent components drive efficient biomass breakdown. Whereas lignin dissociates over a wide temperature range (>25 °C) cellulose disruption occurs only above 150 °C. Neutron scattering with contrast variation provides direct evidence for the formation of THF-rich nanoclusters (Rg ∼ 0.5 nm) on the nonpolar cellulose surfaces and on hydrophobic lignin, and equivalent water-rich nanoclusters on polar cellulose surfaces. The disassembly of the amphiphilic biomass is thus enabled through the local demixing of highly functional cosolvents, THF and water, which preferentially solvate specific biomass surfaces so as to match the local solute polarity. A multiscale description of the efficiency of THF:water pretreatment is provided: matching polarity at the atomic scale prevents lignin aggregation and disrupts cellulose, leading to improvements in deconstruction at the macroscopic scale.

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KW - Pretreatment

KW - Solvents

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JF - Proceedings of the National Academy of Sciences of the United States of America

IS - 29

ER -

Deconstruction of biomass enabled by local demixing of cosolvents at cellulose and lignin surfaces

Abstract

Funding

Keywords

UN SDGs

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