Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures
Autor(a) principal: | |
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Data de Publicação: | 2019 |
Outros Autores: | , |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Repositório Institucional da UNESP |
Texto Completo: | http://dx.doi.org/10.1007/s00894-019-4130-4 http://hdl.handle.net/11449/189414 |
Resumo: | Lignin is one of the most abundant natural materials around the world, accounting for about a quarter of the woody tissue. In general, it is well known that these highly branched aromatic bio-polymers are formed from the polymerization of p-coumaryl, coniferyl, and sinapyl alcohols; however, the connection between these structures are still not known in detail. In this work, we have employed electronic structure calculations to investigate local reactivities and details regarding the connectivity between the basic structures of lignin (unmodified mono and dilignols as well as dehydrogenated monolignols). Condensed-to-atoms Fukui indexes, local softness and hard and soft acids and bases principle were employed in the analyses. The results allow identifying reactive sites on the lignin subunits and access details on the synthesis and degradation of this bio-material. In particular, it is possible to identify a strong influence of the dehydrogenation and monomer dimerization on the monolignols reactivities, which activate the O–C4 and C5 positions. [Figure not available: see fulltext.]. |
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Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structuresDensity functional theoryElectronic structure calculationsLigninLocal reactivityPolymerizationLignin is one of the most abundant natural materials around the world, accounting for about a quarter of the woody tissue. In general, it is well known that these highly branched aromatic bio-polymers are formed from the polymerization of p-coumaryl, coniferyl, and sinapyl alcohols; however, the connection between these structures are still not known in detail. In this work, we have employed electronic structure calculations to investigate local reactivities and details regarding the connectivity between the basic structures of lignin (unmodified mono and dilignols as well as dehydrogenated monolignols). Condensed-to-atoms Fukui indexes, local softness and hard and soft acids and bases principle were employed in the analyses. The results allow identifying reactive sites on the lignin subunits and access details on the synthesis and degradation of this bio-material. In particular, it is possible to identify a strong influence of the dehydrogenation and monomer dimerization on the monolignols reactivities, which activate the O–C4 and C5 positions. [Figure not available: see fulltext.].Campus of Itapeva São Paulo State University (UNESP)Campus of Itapeva São Paulo State University (UNESP)Universidade Estadual Paulista (Unesp)Maia, Rosangela A. [UNESP]Ventorim, Gustavo [UNESP]Batagin-Neto, Augusto [UNESP]2019-10-06T16:39:57Z2019-10-06T16:39:57Z2019-08-01info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/articlehttp://dx.doi.org/10.1007/s00894-019-4130-4Journal of Molecular Modeling, v. 25, n. 8, 2019.0948-50231610-2940http://hdl.handle.net/11449/18941410.1007/s00894-019-4130-42-s2.0-85069189747Scopusreponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengJournal of Molecular Modelinginfo:eu-repo/semantics/openAccess2021-10-22T19:44:47Zoai:repositorio.unesp.br:11449/189414Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T17:24:17.719291Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false |
dc.title.none.fl_str_mv |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
title |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
spellingShingle |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures Maia, Rosangela A. [UNESP] Density functional theory Electronic structure calculations Lignin Local reactivity Polymerization |
title_short |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
title_full |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
title_fullStr |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
title_full_unstemmed |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
title_sort |
Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures |
author |
Maia, Rosangela A. [UNESP] |
author_facet |
Maia, Rosangela A. [UNESP] Ventorim, Gustavo [UNESP] Batagin-Neto, Augusto [UNESP] |
author_role |
author |
author2 |
Ventorim, Gustavo [UNESP] Batagin-Neto, Augusto [UNESP] |
author2_role |
author author |
dc.contributor.none.fl_str_mv |
Universidade Estadual Paulista (Unesp) |
dc.contributor.author.fl_str_mv |
Maia, Rosangela A. [UNESP] Ventorim, Gustavo [UNESP] Batagin-Neto, Augusto [UNESP] |
dc.subject.por.fl_str_mv |
Density functional theory Electronic structure calculations Lignin Local reactivity Polymerization |
topic |
Density functional theory Electronic structure calculations Lignin Local reactivity Polymerization |
description |
Lignin is one of the most abundant natural materials around the world, accounting for about a quarter of the woody tissue. In general, it is well known that these highly branched aromatic bio-polymers are formed from the polymerization of p-coumaryl, coniferyl, and sinapyl alcohols; however, the connection between these structures are still not known in detail. In this work, we have employed electronic structure calculations to investigate local reactivities and details regarding the connectivity between the basic structures of lignin (unmodified mono and dilignols as well as dehydrogenated monolignols). Condensed-to-atoms Fukui indexes, local softness and hard and soft acids and bases principle were employed in the analyses. The results allow identifying reactive sites on the lignin subunits and access details on the synthesis and degradation of this bio-material. In particular, it is possible to identify a strong influence of the dehydrogenation and monomer dimerization on the monolignols reactivities, which activate the O–C4 and C5 positions. [Figure not available: see fulltext.]. |
publishDate |
2019 |
dc.date.none.fl_str_mv |
2019-10-06T16:39:57Z 2019-10-06T16:39:57Z 2019-08-01 |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://dx.doi.org/10.1007/s00894-019-4130-4 Journal of Molecular Modeling, v. 25, n. 8, 2019. 0948-5023 1610-2940 http://hdl.handle.net/11449/189414 10.1007/s00894-019-4130-4 2-s2.0-85069189747 |
url |
http://dx.doi.org/10.1007/s00894-019-4130-4 http://hdl.handle.net/11449/189414 |
identifier_str_mv |
Journal of Molecular Modeling, v. 25, n. 8, 2019. 0948-5023 1610-2940 10.1007/s00894-019-4130-4 2-s2.0-85069189747 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
Journal of Molecular Modeling |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.source.none.fl_str_mv |
Scopus reponame:Repositório Institucional da UNESP instname:Universidade Estadual Paulista (UNESP) instacron:UNESP |
instname_str |
Universidade Estadual Paulista (UNESP) |
instacron_str |
UNESP |
institution |
UNESP |
reponame_str |
Repositório Institucional da UNESP |
collection |
Repositório Institucional da UNESP |
repository.name.fl_str_mv |
Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP) |
repository.mail.fl_str_mv |
|
_version_ |
1808128805075681280 |