The role of weak interactions in lignin polymerization
Lignin is the most abundant natural polymer composed by aromatic moieties. Its chemical composition and its abundance have focused efforts to unlock its potential as a source of aromatic compounds for many years. The lack of a proper way for lignin de-polymerization has hampered its success as a nat...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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Springer Berlin Heidelberg
2017
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| Online Access: | http://hdl.handle.net/1721.1/107002 |
| _version_ | 1826205031564574720 |
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| author | Sánchez-González, Ángel Dobado, J. A. Martin-Martinez, Francisco J. |
| author2 | Massachusetts Institute of Technology. Department of Civil and Environmental Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Sánchez-González, Ángel Dobado, J. A. Martin-Martinez, Francisco J. |
| author_sort | Sánchez-González, Ángel |
| collection | MIT |
| description | Lignin is the most abundant natural polymer composed by aromatic moieties. Its chemical composition and its abundance have focused efforts to unlock its potential as a source of aromatic compounds for many years. The lack of a proper way for lignin de-polymerization has hampered its success as a natural solution for commodity aromatic chemicals, which is also due to the lack of understanding of the underlying mechanisms of lignin polymerization. A fuller fundamental understanding of polymerization mechanisms could lead to improvements in de-polymerization strategies, and therefore a proper methodology and a predictive theoretical framework are required for such purpose. This work presents a complete computational study on some of the key steps of lignin polymerization mechanisms. Density functional theory (DFT) calculations have been performed to evaluate the most appropriate methodology and to compute the chemical structures and reaction enthalpies for the monolignol dimerization, the simplest key step that controls the polymerization. Quantum theory of atoms in molecules (QTAIM) has been applied to understand the coupling reaction mechanisms, for which the radical species and transition states (TSs) involved have been characterized. The coupling that leads to the formation of the β–O–4 linkage has been theoretically reproduced according to proposed mechanisms, for which weak interactions have been found to play a key role in the arrangement of reactants. The hydrogen bond formed between the oxygen of the phenoxy radical, and the alcohol of the aliphatic chain, together with the interaction between aromatic rings, locates the reactants in a position that favors such β–O–4 linkage.
Graphical Abstract
QTAIM analysis of the complex between coumaryl and coniferyl alcohols. It emphasizes the importance of weak interactions during the formation of beta-O-4 linkages in the polymerization of lignin. |
| first_indexed | 2024-09-23T13:05:59Z |
| format | Article |
| id | mit-1721.1/107002 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T13:05:59Z |
| publishDate | 2017 |
| publisher | Springer Berlin Heidelberg |
| record_format | dspace |
| spelling | mit-1721.1/1070022022-09-28T12:00:32Z The role of weak interactions in lignin polymerization Sánchez-González, Ángel Dobado, J. A. Martin-Martinez, Francisco J. Massachusetts Institute of Technology. Department of Civil and Environmental Engineering Martin-Martinez, Francisco J. Lignin is the most abundant natural polymer composed by aromatic moieties. Its chemical composition and its abundance have focused efforts to unlock its potential as a source of aromatic compounds for many years. The lack of a proper way for lignin de-polymerization has hampered its success as a natural solution for commodity aromatic chemicals, which is also due to the lack of understanding of the underlying mechanisms of lignin polymerization. A fuller fundamental understanding of polymerization mechanisms could lead to improvements in de-polymerization strategies, and therefore a proper methodology and a predictive theoretical framework are required for such purpose. This work presents a complete computational study on some of the key steps of lignin polymerization mechanisms. Density functional theory (DFT) calculations have been performed to evaluate the most appropriate methodology and to compute the chemical structures and reaction enthalpies for the monolignol dimerization, the simplest key step that controls the polymerization. Quantum theory of atoms in molecules (QTAIM) has been applied to understand the coupling reaction mechanisms, for which the radical species and transition states (TSs) involved have been characterized. The coupling that leads to the formation of the β–O–4 linkage has been theoretically reproduced according to proposed mechanisms, for which weak interactions have been found to play a key role in the arrangement of reactants. The hydrogen bond formed between the oxygen of the phenoxy radical, and the alcohol of the aliphatic chain, together with the interaction between aromatic rings, locates the reactants in a position that favors such β–O–4 linkage. Graphical Abstract QTAIM analysis of the complex between coumaryl and coniferyl alcohols. It emphasizes the importance of weak interactions during the formation of beta-O-4 linkages in the polymerization of lignin. Ecuador. Secretaría de Educación Superior, Ciencia, Tecnología e Innovación. Proyecto Prometeo 2017-02-21T16:11:02Z 2017-12-03T06:00:04Z 2017-02 2017-02-17T04:37:46Z Article http://purl.org/eprint/type/JournalArticle 1610-2940 0948-5023 http://hdl.handle.net/1721.1/107002 Sánchez-González, Ángel, Francisco J. Martín-Martínez, and J. A. Dobado. “The Role of Weak Interactions in Lignin Polymerization.” Journal of Molecular Modeling 23.3 (2017): n. pag. en http://dx.doi.org/10.1007/s00894-017-3257-4 Journal of Molecular Modeling Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. Springer-Verlag Berlin Heidelberg application/pdf Springer Berlin Heidelberg Springer Berlin Heidelberg |
| spellingShingle | Sánchez-González, Ángel Dobado, J. A. Martin-Martinez, Francisco J. The role of weak interactions in lignin polymerization |
| title | The role of weak interactions in lignin polymerization |
| title_full | The role of weak interactions in lignin polymerization |
| title_fullStr | The role of weak interactions in lignin polymerization |
| title_full_unstemmed | The role of weak interactions in lignin polymerization |
| title_short | The role of weak interactions in lignin polymerization |
| title_sort | role of weak interactions in lignin polymerization |
| url | http://hdl.handle.net/1721.1/107002 |
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