Towards understanding of delignification of grassy and woody biomass in cholinium-based ionic liquids

Mood Mohan; Hemant Choudhary; Anthe George; Blake A. Simmons; Kenneth Sale; John M. Gladden

doi:10.1039/d1gc01622a

Towards understanding of delignification of grassy and woody biomass in cholinium-based ionic liquids

Mood Mohan, Hemant Choudhary, Anthe George, Blake A. Simmons, Kenneth Sale, John M. Gladden

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28 Scopus citations

Abstract

The molecular level details of dissolution of lignin in certain ionic liquids (ILs), such as cholinium-based ILs, are a relatively underexplored area and several key details to comprehend the dissolution mechanism are yet to be discovered. To understand, answer, and connect the missing links in the delignification mechanism during biomass pretreatment using cholinium-based ILs we employ COnductor like Screening MOdel for Real Solvents (COSMO-RS) and molecular dynamics (MD) simulations to evaluate the interactions between lignin-like model compounds and the anion and cation of several cholinium-based ILs. Initially, lignin dissolution was studied for cholinium-based ILs containing five different carboxylate anions ([For], [Ace], [But], [Hex], and [Oct]) and were compared with lysinate as the anion. The microscopic properties such as interaction energies, activity coefficient, radial and spatial distribution functions (RDF/SDF), and hydrogen bonds and their dynamics were assessed to characterize lignin dissolution in these ILs and were validated with experimental data. Among the anions studied, both octanoate and lysinate containing ILs demonstrated better lignin dissolution; lysinate being the best. The simulation data suggested that [Ch][Lys] has higher affinity for ether linkages of lignin (e.g., β-O-4) than for C-C linkages, which explains the higher delignification of hardwood and grassy biomasses (60-80% C-O-C linkages) in [Ch][Lys].

Original language	English
Pages (from-to)	6020-6035
Number of pages	16
Journal	Green Chemistry
Volume	23
Issue number	16
DOIs	https://doi.org/10.1039/d1gc01622a
State	Published - Aug 21 2021
Externally published	Yes

Funding

This work was part of the DOE Joint BioEnergy Institute (http://www.jbei.org) supported by the U. S. Department of Energy, Office of Science, Office of Biological and Environmental Research, through contract DE-AC02-05CH11231 between Lawrence Berkeley National Laboratory and the U. S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

Funders	Funder number
U.S. Department of Energy
Office of Science
Biological and Environmental Research	DE-AC02-05CH11231
Lawrence Berkeley National Laboratory

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title = "Towards understanding of delignification of grassy and woody biomass in cholinium-based ionic liquids",

abstract = "The molecular level details of dissolution of lignin in certain ionic liquids (ILs), such as cholinium-based ILs, are a relatively underexplored area and several key details to comprehend the dissolution mechanism are yet to be discovered. To understand, answer, and connect the missing links in the delignification mechanism during biomass pretreatment using cholinium-based ILs we employ COnductor like Screening MOdel for Real Solvents (COSMO-RS) and molecular dynamics (MD) simulations to evaluate the interactions between lignin-like model compounds and the anion and cation of several cholinium-based ILs. Initially, lignin dissolution was studied for cholinium-based ILs containing five different carboxylate anions ([For], [Ace], [But], [Hex], and [Oct]) and were compared with lysinate as the anion. The microscopic properties such as interaction energies, activity coefficient, radial and spatial distribution functions (RDF/SDF), and hydrogen bonds and their dynamics were assessed to characterize lignin dissolution in these ILs and were validated with experimental data. Among the anions studied, both octanoate and lysinate containing ILs demonstrated better lignin dissolution; lysinate being the best. The simulation data suggested that [Ch][Lys] has higher affinity for ether linkages of lignin (e.g., β-O-4) than for C-C linkages, which explains the higher delignification of hardwood and grassy biomasses (60-80% C-O-C linkages) in [Ch][Lys].",

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AU - Sale, Kenneth

AU - Gladden, John M.

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AB - The molecular level details of dissolution of lignin in certain ionic liquids (ILs), such as cholinium-based ILs, are a relatively underexplored area and several key details to comprehend the dissolution mechanism are yet to be discovered. To understand, answer, and connect the missing links in the delignification mechanism during biomass pretreatment using cholinium-based ILs we employ COnductor like Screening MOdel for Real Solvents (COSMO-RS) and molecular dynamics (MD) simulations to evaluate the interactions between lignin-like model compounds and the anion and cation of several cholinium-based ILs. Initially, lignin dissolution was studied for cholinium-based ILs containing five different carboxylate anions ([For], [Ace], [But], [Hex], and [Oct]) and were compared with lysinate as the anion. The microscopic properties such as interaction energies, activity coefficient, radial and spatial distribution functions (RDF/SDF), and hydrogen bonds and their dynamics were assessed to characterize lignin dissolution in these ILs and were validated with experimental data. Among the anions studied, both octanoate and lysinate containing ILs demonstrated better lignin dissolution; lysinate being the best. The simulation data suggested that [Ch][Lys] has higher affinity for ether linkages of lignin (e.g., β-O-4) than for C-C linkages, which explains the higher delignification of hardwood and grassy biomasses (60-80% C-O-C linkages) in [Ch][Lys].

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Towards understanding of delignification of grassy and woody biomass in cholinium-based ionic liquids

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