Rotational isomers of lactic acid: First experimental observation of higher energy forms

Autores
Borba, Ana; Gomez Zavaglia, Andrea; Lapinski, Leszek; Fausto, R.
Año de publicación
2004
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Lactic acid {2-hydroxypropionic acid [CH(CH3)OHCOOH]} monomer was studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at both DFT(B3LYP)/6-311++G(d,p) and MP2/ 6-31G(d,p) levels of approximation. The theoretical calculations predicted the conformer (SsC) with the carboxylic group and both the CCOH(alcohol) and O=CCO moieties in a cis configuration as the most stable form. In this conformer, the α-hydroxy hydrogen atom is involved in an intramolecular hydrogen bond with the carbonyl oxygen atom. The second most stable conformer (GskC) also shows a cis carboxylic group and differs from SsC in the CCOH (alcohol) and O=CCO dihedral angles, which are equal to 43.3° and 156.8° respectively. These angles are equal to -51.5° and -149.9° in the third most stable conformer (G′sk′C). These forms are characterized by showing a relatively weak intramolecular H (alcohol)⋯O(acid) hydrogen bond. In the AaT conformer, the carboxylic group is trans and the CCOH(alcohol) and O=CCO dihedral angles are 162.2° and 174.1°, respectively. This conformer shows a relatively strong H(acid)⋯O (alcohol) hydrogen bond. In consonance with the theoretical results, the matrix isolation experiments confirmed the predominance of conformer SsC in argon and xenon matrices, and provide the first experimental evidence of conformers GskC and AaT. Since the barrier for interconversion G′sk′C ↔ GskC is only ∼2 kJ mol-1, these two conformers are in equilibrium in the matrices and, at low temperature, the population of the less stable G′sk′C form is too small to enable its observation. Full assignment of the observed spectra was undertaken on the basis of comparison with the theoretical data and temperature variation studies. Water doping of matrices enabled the identification of spectral features due to weakly bound complexes of lactic acid with water.
Fil: Borba, Ana. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Lapinski, Leszek. Institute Of Physics Of The Polish Academy Of Sciences; Polonia
Fil: Fausto, R.. Universidad de Coimbra; Portugal
Materia
FTIR
ACTIC ACID
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/151923
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/151923
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Rotational isomers of lactic acid: First experimental observation of higher energy formsBorba, AnaGomez Zavaglia, AndreaLapinski, LeszekFausto, R.FTIRACTIC ACIDhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2Lactic acid {2-hydroxypropionic acid [CH(CH3)OHCOOH]} monomer was studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at both DFT(B3LYP)/6-311++G(d,p) and MP2/ 6-31G(d,p) levels of approximation. The theoretical calculations predicted the conformer (SsC) with the carboxylic group and both the CCOH(alcohol) and O=CCO moieties in a cis configuration as the most stable form. In this conformer, the α-hydroxy hydrogen atom is involved in an intramolecular hydrogen bond with the carbonyl oxygen atom. The second most stable conformer (GskC) also shows a cis carboxylic group and differs from SsC in the CCOH (alcohol) and O=CCO dihedral angles, which are equal to 43.3° and 156.8° respectively. These angles are equal to -51.5° and -149.9° in the third most stable conformer (G′sk′C). These forms are characterized by showing a relatively weak intramolecular H (alcohol)⋯O(acid) hydrogen bond. In the AaT conformer, the carboxylic group is trans and the CCOH(alcohol) and O=CCO dihedral angles are 162.2° and 174.1°, respectively. This conformer shows a relatively strong H(acid)⋯O (alcohol) hydrogen bond. In consonance with the theoretical results, the matrix isolation experiments confirmed the predominance of conformer SsC in argon and xenon matrices, and provide the first experimental evidence of conformers GskC and AaT. Since the barrier for interconversion G′sk′C ↔ GskC is only ∼2 kJ mol-1, these two conformers are in equilibrium in the matrices and, at low temperature, the population of the less stable G′sk′C form is too small to enable its observation. Full assignment of the observed spectra was undertaken on the basis of comparison with the theoretical data and temperature variation studies. Water doping of matrices enabled the identification of spectral features due to weakly bound complexes of lactic acid with water.Fil: Borba, Ana. Universidad de Coimbra; PortugalFil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaFil: Lapinski, Leszek. Institute Of Physics Of The Polish Academy Of Sciences; PoloniaFil: Fausto, R.. Universidad de Coimbra; PortugalRoyal Society of Chemistry2004-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/151923Borba, Ana; Gomez Zavaglia, Andrea; Lapinski, Leszek; Fausto, R.; Rotational isomers of lactic acid: First experimental observation of higher energy forms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 6; 9; 12-2004; 2101-21081463-90761463-9084CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1039/b316642binfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2004/cp/b316642binfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:29:38Zoai:ri.conicet.gov.ar:11336/151923instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 10:29:39.073CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Rotational isomers of lactic acid: First experimental observation of higher energy forms
title Rotational isomers of lactic acid: First experimental observation of higher energy forms
spellingShingle Rotational isomers of lactic acid: First experimental observation of higher energy forms
Borba, Ana
FTIR
ACTIC ACID
title_short Rotational isomers of lactic acid: First experimental observation of higher energy forms
title_full Rotational isomers of lactic acid: First experimental observation of higher energy forms
title_fullStr Rotational isomers of lactic acid: First experimental observation of higher energy forms
title_full_unstemmed Rotational isomers of lactic acid: First experimental observation of higher energy forms
title_sort Rotational isomers of lactic acid: First experimental observation of higher energy forms
dc.creator.none.fl_str_mv Borba, Ana
Gomez Zavaglia, Andrea
Lapinski, Leszek
Fausto, R.
author Borba, Ana
author_facet Borba, Ana
Gomez Zavaglia, Andrea
Lapinski, Leszek
Fausto, R.
author_role author
author2 Gomez Zavaglia, Andrea
Lapinski, Leszek
Fausto, R.
author2_role author
author
author
dc.subject.none.fl_str_mv FTIR
ACTIC ACID
topic FTIR
ACTIC ACID
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv Lactic acid {2-hydroxypropionic acid [CH(CH3)OHCOOH]} monomer was studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at both DFT(B3LYP)/6-311++G(d,p) and MP2/ 6-31G(d,p) levels of approximation. The theoretical calculations predicted the conformer (SsC) with the carboxylic group and both the CCOH(alcohol) and O=CCO moieties in a cis configuration as the most stable form. In this conformer, the α-hydroxy hydrogen atom is involved in an intramolecular hydrogen bond with the carbonyl oxygen atom. The second most stable conformer (GskC) also shows a cis carboxylic group and differs from SsC in the CCOH (alcohol) and O=CCO dihedral angles, which are equal to 43.3° and 156.8° respectively. These angles are equal to -51.5° and -149.9° in the third most stable conformer (G′sk′C). These forms are characterized by showing a relatively weak intramolecular H (alcohol)⋯O(acid) hydrogen bond. In the AaT conformer, the carboxylic group is trans and the CCOH(alcohol) and O=CCO dihedral angles are 162.2° and 174.1°, respectively. This conformer shows a relatively strong H(acid)⋯O (alcohol) hydrogen bond. In consonance with the theoretical results, the matrix isolation experiments confirmed the predominance of conformer SsC in argon and xenon matrices, and provide the first experimental evidence of conformers GskC and AaT. Since the barrier for interconversion G′sk′C ↔ GskC is only ∼2 kJ mol-1, these two conformers are in equilibrium in the matrices and, at low temperature, the population of the less stable G′sk′C form is too small to enable its observation. Full assignment of the observed spectra was undertaken on the basis of comparison with the theoretical data and temperature variation studies. Water doping of matrices enabled the identification of spectral features due to weakly bound complexes of lactic acid with water.
Fil: Borba, Ana. Universidad de Coimbra; Portugal
Fil: Gomez Zavaglia, Andrea. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Fil: Lapinski, Leszek. Institute Of Physics Of The Polish Academy Of Sciences; Polonia
Fil: Fausto, R.. Universidad de Coimbra; Portugal
description Lactic acid {2-hydroxypropionic acid [CH(CH3)OHCOOH]} monomer was studied by matrix isolation FT-IR spectroscopy and molecular orbital calculations undertaken at both DFT(B3LYP)/6-311++G(d,p) and MP2/ 6-31G(d,p) levels of approximation. The theoretical calculations predicted the conformer (SsC) with the carboxylic group and both the CCOH(alcohol) and O=CCO moieties in a cis configuration as the most stable form. In this conformer, the α-hydroxy hydrogen atom is involved in an intramolecular hydrogen bond with the carbonyl oxygen atom. The second most stable conformer (GskC) also shows a cis carboxylic group and differs from SsC in the CCOH (alcohol) and O=CCO dihedral angles, which are equal to 43.3° and 156.8° respectively. These angles are equal to -51.5° and -149.9° in the third most stable conformer (G′sk′C). These forms are characterized by showing a relatively weak intramolecular H (alcohol)⋯O(acid) hydrogen bond. In the AaT conformer, the carboxylic group is trans and the CCOH(alcohol) and O=CCO dihedral angles are 162.2° and 174.1°, respectively. This conformer shows a relatively strong H(acid)⋯O (alcohol) hydrogen bond. In consonance with the theoretical results, the matrix isolation experiments confirmed the predominance of conformer SsC in argon and xenon matrices, and provide the first experimental evidence of conformers GskC and AaT. Since the barrier for interconversion G′sk′C ↔ GskC is only ∼2 kJ mol-1, these two conformers are in equilibrium in the matrices and, at low temperature, the population of the less stable G′sk′C form is too small to enable its observation. Full assignment of the observed spectra was undertaken on the basis of comparison with the theoretical data and temperature variation studies. Water doping of matrices enabled the identification of spectral features due to weakly bound complexes of lactic acid with water.
publishDate 2004
dc.date.none.fl_str_mv 2004-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/151923
Borba, Ana; Gomez Zavaglia, Andrea; Lapinski, Leszek; Fausto, R.; Rotational isomers of lactic acid: First experimental observation of higher energy forms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 6; 9; 12-2004; 2101-2108
1463-9076
1463-9084
CONICET Digital
CONICET
url http://hdl.handle.net/11336/151923
identifier_str_mv Borba, Ana; Gomez Zavaglia, Andrea; Lapinski, Leszek; Fausto, R.; Rotational isomers of lactic acid: First experimental observation of higher energy forms; Royal Society of Chemistry; Physical Chemistry Chemical Physics; 6; 9; 12-2004; 2101-2108
1463-9076
1463-9084
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1039/b316642b
info:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/content/articlelanding/2004/cp/b316642b
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.070432

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