Reactivity of lignin subunits: the influence of dehydrogenation and formation of dimeric structures

Detalhes bibliográficos
Autor(a) principal: Maia, Rosangela A. [UNESP]
Data de Publicação: 2019
Outros Autores: Ventorim, Gustavo [UNESP], Batagin-Neto, Augusto [UNESP]
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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spelling 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
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