The multiscale solvation effect on the reactivity of β-O-4 of lignin dimers in deep eutectic solvents

Qi Qiao; Jian Shi; Qing Shao

doi:10.1039/d1cp04342k

The multiscale solvation effect on the reactivity of β-O-4 of lignin dimers in deep eutectic solvents

Qi Qiao
, Jian Shi
, Qing Shao

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

12 Scopus citations

Abstract

Deep eutectic solvents (DESs) emerge as a medium to enhance the depolymerization of lignin. One critical question is how the solvation of lignin in DESs may affect the reactivity of lignin. To shed light on this question, we investigate the solvation of four lignin dimers in three DES solutions using molecular dynamics simulations and quantum mechanical calculations. The four lignin dimers are composed of guaiacyl and syringyl units and are used as the models for lignin. The three DES solutions are composed of choline, Cl- and three acids: lactic acid, levulinic acid and oxalic acid. We investigate the preferential accumulation of individual DES components in the solvation shells and the exposure area and electrostatic potential of the β-O-4 linkage of the four lignin dimers in the three DESs. The results show that DESs could influence the affinity and nucleophilicity of the β-O-4 linkage through three effects: (1) forming a charged solvation shell, (2) varying the exposure of the β-O-4 linkage and (3) adjusting the electrostatic potential of the β-O-4 linkage. Our simulations indicate a comprehensive and multiscale effect of DESs on lignin decomposition.

Original language	English
Pages (from-to)	25699-25705
Number of pages	7
Journal	Physical Chemistry Chemical Physics
Volume	23
Issue number	45
DOIs	https://doi.org/10.1039/d1cp04342k
State	Published - Dec 7 2021

Bibliographical note

Publisher Copyright:
© the Owner Societies.

Funding

Qi Qiao and Qing Shao acknowledge the support from the Startup Funds of the University of Kentucky. Jian Shi acknowledges the support from the National Science Foundation under Cooperative Agreement No. 1632854 and the National Institute of Food and Agriculture, U.S. Department of Agriculture, Sustainability Challenge Area grant under accession number 1015068. We would like to thank the University of Kentucky Center for Computational Sciences and Information Technology Services Research Computing for their support and use of the Lipscomb Compute Cluster and associated research computing resources.

Funders	Funder number
U.S. Department of Energy Chinese Academy of Sciences Guangzhou Municipal Science and Technology Project Oak Ridge National Laboratory Extreme Science and Engineering Discovery Environment National Science Foundation National Energy Research Scientific Computing Center National Natural Science Foundation of China	1632854
U.S. Department of Energy Chinese Academy of Sciences Guangzhou Municipal Science and Technology Project Oak Ridge National Laboratory Extreme Science and Engineering Discovery Environment National Science Foundation National Energy Research Scientific Computing Center National Natural Science Foundation of China
U.S. Department of Agriculture	1015068
U.S. Department of Agriculture
US Department of Agriculture National Institute of Food and Agriculture, Agriculture and Food Research Initiative
University of Kentucky

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1039/d1cp04342k

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title = "The multiscale solvation effect on the reactivity of β-O-4 of lignin dimers in deep eutectic solvents",

abstract = "Deep eutectic solvents (DESs) emerge as a medium to enhance the depolymerization of lignin. One critical question is how the solvation of lignin in DESs may affect the reactivity of lignin. To shed light on this question, we investigate the solvation of four lignin dimers in three DES solutions using molecular dynamics simulations and quantum mechanical calculations. The four lignin dimers are composed of guaiacyl and syringyl units and are used as the models for lignin. The three DES solutions are composed of choline, Cl- and three acids: lactic acid, levulinic acid and oxalic acid. We investigate the preferential accumulation of individual DES components in the solvation shells and the exposure area and electrostatic potential of the β-O-4 linkage of the four lignin dimers in the three DESs. The results show that DESs could influence the affinity and nucleophilicity of the β-O-4 linkage through three effects: (1) forming a charged solvation shell, (2) varying the exposure of the β-O-4 linkage and (3) adjusting the electrostatic potential of the β-O-4 linkage. Our simulations indicate a comprehensive and multiscale effect of DESs on lignin decomposition.",

author = "Qi Qiao and Jian Shi and Qing Shao",

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AU - Qiao, Qi

AU - Shi, Jian

AU - Shao, Qing

N1 - Publisher Copyright: © the Owner Societies.

PY - 2021/12/7

Y1 - 2021/12/7

N2 - Deep eutectic solvents (DESs) emerge as a medium to enhance the depolymerization of lignin. One critical question is how the solvation of lignin in DESs may affect the reactivity of lignin. To shed light on this question, we investigate the solvation of four lignin dimers in three DES solutions using molecular dynamics simulations and quantum mechanical calculations. The four lignin dimers are composed of guaiacyl and syringyl units and are used as the models for lignin. The three DES solutions are composed of choline, Cl- and three acids: lactic acid, levulinic acid and oxalic acid. We investigate the preferential accumulation of individual DES components in the solvation shells and the exposure area and electrostatic potential of the β-O-4 linkage of the four lignin dimers in the three DESs. The results show that DESs could influence the affinity and nucleophilicity of the β-O-4 linkage through three effects: (1) forming a charged solvation shell, (2) varying the exposure of the β-O-4 linkage and (3) adjusting the electrostatic potential of the β-O-4 linkage. Our simulations indicate a comprehensive and multiscale effect of DESs on lignin decomposition.

AB - Deep eutectic solvents (DESs) emerge as a medium to enhance the depolymerization of lignin. One critical question is how the solvation of lignin in DESs may affect the reactivity of lignin. To shed light on this question, we investigate the solvation of four lignin dimers in three DES solutions using molecular dynamics simulations and quantum mechanical calculations. The four lignin dimers are composed of guaiacyl and syringyl units and are used as the models for lignin. The three DES solutions are composed of choline, Cl- and three acids: lactic acid, levulinic acid and oxalic acid. We investigate the preferential accumulation of individual DES components in the solvation shells and the exposure area and electrostatic potential of the β-O-4 linkage of the four lignin dimers in the three DESs. The results show that DESs could influence the affinity and nucleophilicity of the β-O-4 linkage through three effects: (1) forming a charged solvation shell, (2) varying the exposure of the β-O-4 linkage and (3) adjusting the electrostatic potential of the β-O-4 linkage. Our simulations indicate a comprehensive and multiscale effect of DESs on lignin decomposition.

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The multiscale solvation effect on the reactivity of β-O-4 of lignin dimers in deep eutectic solvents

Abstract

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