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Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT)
Model compounds that represent important substructures in lignin have popularly been used to gain a better understanding of the behavior of lignin during thermal deconstruction, such as fast pyrolysis. The β-O-4 linkage of lignin has previously been the focus of many model compound studies as it is...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2023
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9941757/ https://www.ncbi.nlm.nih.gov/pubmed/36825296 http://dx.doi.org/10.1039/d2ra07787f |
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author | Houston, Ross W. Abdoulmoumine, Nourredine H. |
author_facet | Houston, Ross W. Abdoulmoumine, Nourredine H. |
author_sort | Houston, Ross W. |
collection | PubMed |
description | Model compounds that represent important substructures in lignin have popularly been used to gain a better understanding of the behavior of lignin during thermal deconstruction, such as fast pyrolysis. The β-O-4 linkage of lignin has previously been the focus of many model compound studies as it is the most prevalent linkage found in native lignin. In this work, two lesser studied linkages, the β–β′ and 4-O-5, were investigated with density functional theory (DFT). Bond dissociation enthalpies (BDEs) were calculated for the relevant bonds along each interunit linkage for two model compounds containing these linkages. Conformational analysis of the first model oligomer has a relative enthalpy difference of 1.55 kcal mol(−1). For the β–β′ linkage, the alpha carbons had the lowest BDEs of the ring opening reactions due to excessive electron delocalization around the aromatic rings. The bonds of the 4-O-5 linkage had similar BDEs but were appreciably higher than the BDEs for other ether linkages, such as β-O-4 and α-O-4. The higher BDEs of the 4-O-5 bonds is a result of the radical being formed on an aromatic carbon compared to an aliphatic carbon. Our results indicate the ring-opening reactions around the alpha-carbon of the β–β′ linkage would be a major reaction point during thermal deconstruction of the chosen oligomers. This work provides valuable information on the thermal deconstruction behavior of two lesser studied interunit linkages that builds on the authors' previous work, on β-O-4, α-O-4, and β-5 linkages, to develop a library of reaction information for various lignin interunit linkages. |
format | Online Article Text |
id | pubmed-9941757 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-99417572023-02-22 Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) Houston, Ross W. Abdoulmoumine, Nourredine H. RSC Adv Chemistry Model compounds that represent important substructures in lignin have popularly been used to gain a better understanding of the behavior of lignin during thermal deconstruction, such as fast pyrolysis. The β-O-4 linkage of lignin has previously been the focus of many model compound studies as it is the most prevalent linkage found in native lignin. In this work, two lesser studied linkages, the β–β′ and 4-O-5, were investigated with density functional theory (DFT). Bond dissociation enthalpies (BDEs) were calculated for the relevant bonds along each interunit linkage for two model compounds containing these linkages. Conformational analysis of the first model oligomer has a relative enthalpy difference of 1.55 kcal mol(−1). For the β–β′ linkage, the alpha carbons had the lowest BDEs of the ring opening reactions due to excessive electron delocalization around the aromatic rings. The bonds of the 4-O-5 linkage had similar BDEs but were appreciably higher than the BDEs for other ether linkages, such as β-O-4 and α-O-4. The higher BDEs of the 4-O-5 bonds is a result of the radical being formed on an aromatic carbon compared to an aliphatic carbon. Our results indicate the ring-opening reactions around the alpha-carbon of the β–β′ linkage would be a major reaction point during thermal deconstruction of the chosen oligomers. This work provides valuable information on the thermal deconstruction behavior of two lesser studied interunit linkages that builds on the authors' previous work, on β-O-4, α-O-4, and β-5 linkages, to develop a library of reaction information for various lignin interunit linkages. The Royal Society of Chemistry 2023-02-21 /pmc/articles/PMC9941757/ /pubmed/36825296 http://dx.doi.org/10.1039/d2ra07787f Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/ |
spellingShingle | Chemistry Houston, Ross W. Abdoulmoumine, Nourredine H. Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) |
title | Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) |
title_full | Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) |
title_fullStr | Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) |
title_full_unstemmed | Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) |
title_short | Investigation of the thermal deconstruction of β–β′ and 4-O-5 linkages in lignin model oligomers by density functional theory (DFT) |
title_sort | investigation of the thermal deconstruction of β–β′ and 4-o-5 linkages in lignin model oligomers by density functional theory (dft) |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9941757/ https://www.ncbi.nlm.nih.gov/pubmed/36825296 http://dx.doi.org/10.1039/d2ra07787f |
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