Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase

Autores
Borba, Ana; Albrecht, Claudia; Gomez Zavaglia, Andrea; Suhm, Martin A.; Fausto, Rui
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
A structural and spectroscopic analysis of the anti-tuberculosis drug pyrazinamide (PZA) was carried out. The PZA molecule was predicted theoretically to possess two conformers differing by internal rotation around the C - C(=O) bond, with the E conformer (Cs symmetry point group; N - C - C=O dihedral: 180°) being ca. 30 kJ mol-1 more stable than the Z form (C 1 point group; N - C - C=O dihedral: ca. ± 42°). In consonance with both the large energy difference and low energy barrier between the Z and E conformers, upon isolation in low temperature argon and xenon matrices, only the E form could be observed and characterized spectroscopically. In the argon matrix, this conformer was found to exist in at least three matrix sites, of different stability. In a supersonic jet, besides the monomer (E), the most stable dimer of PZA with two equivalent NH O= hydrogen bonds could also be identified. Its spectrum reveals rapid energy flow out of the excited NH stretching mode mediated by one of the heteroatoms in the ring. Finally, the IR spectra of the amorphous solid resulting from fast cooling of the vapor of the compound (initially in the a crystalline phase) onto the cold substrate of the cryostat (10 K) and of the crystalline phase resulting from warming the amorphous solid were also recorded and interpreted. The obtained crystalline phase was found to be the thermodynamically most stable δ polymorph of PZA.
Fil: Borba, Ana. Universidad de Coimbra; Portugal
Fil: Albrecht, Claudia. Universität Göttingen; Alemania
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. Universidad de Coimbra; Portugal
Fil: Suhm, Martin A.. Universität Göttingen; Alemania
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
Materia
Pyrazinamide
Infrared Spectroscopy
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:11336/131247
Acceder
id CONICETDig_c417de7f755e22c083c8eddefbedd7f1
oai_identifier_str oai:ri.conicet.gov.ar:11336/131247
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline PhaseBorba, AnaAlbrecht, ClaudiaGomez Zavaglia, AndreaSuhm, Martin A.Fausto, RuiPyrazinamideInfrared Spectroscopyhttps://purl.org/becyt/ford/2.11https://purl.org/becyt/ford/2A structural and spectroscopic analysis of the anti-tuberculosis drug pyrazinamide (PZA) was carried out. The PZA molecule was predicted theoretically to possess two conformers differing by internal rotation around the C - C(=O) bond, with the E conformer (Cs symmetry point group; N - C - C=O dihedral: 180°) being ca. 30 kJ mol-1 more stable than the Z form (C 1 point group; N - C - C=O dihedral: ca. ± 42°). In consonance with both the large energy difference and low energy barrier between the Z and E conformers, upon isolation in low temperature argon and xenon matrices, only the E form could be observed and characterized spectroscopically. In the argon matrix, this conformer was found to exist in at least three matrix sites, of different stability. In a supersonic jet, besides the monomer (E), the most stable dimer of PZA with two equivalent NH O= hydrogen bonds could also be identified. Its spectrum reveals rapid energy flow out of the excited NH stretching mode mediated by one of the heteroatoms in the ring. Finally, the IR spectra of the amorphous solid resulting from fast cooling of the vapor of the compound (initially in the a crystalline phase) onto the cold substrate of the cryostat (10 K) and of the crystalline phase resulting from warming the amorphous solid were also recorded and interpreted. The obtained crystalline phase was found to be the thermodynamically most stable δ polymorph of PZA.Fil: Borba, Ana. Universidad de Coimbra; PortugalFil: Albrecht, Claudia. Universität Göttingen; AlemaniaFil: 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. Universidad de Coimbra; PortugalFil: Suhm, Martin A.. Universität Göttingen; AlemaniaFil: Fausto, Rui. Universidad de Coimbra; PortugalAmerican Chemical Society2010-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/131247Borba, Ana; Albrecht, Claudia; Gomez Zavaglia, Andrea; Suhm, Martin A.; Fausto, Rui; Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase; American Chemical Society; Journal of Physical Chemistry A; 114; 1; 1-2010; 151-1611089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp907466hinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp907466hinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:03:32Zoai:ri.conicet.gov.ar:11336/131247instacron: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:34982025-09-03 10:03:32.846CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
title Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
spellingShingle Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
Borba, Ana
Pyrazinamide
Infrared Spectroscopy
title_short Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
title_full Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
title_fullStr Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
title_full_unstemmed Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
title_sort Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase
dc.creator.none.fl_str_mv Borba, Ana
Albrecht, Claudia
Gomez Zavaglia, Andrea
Suhm, Martin A.
Fausto, Rui
author Borba, Ana
author_facet Borba, Ana
Albrecht, Claudia
Gomez Zavaglia, Andrea
Suhm, Martin A.
Fausto, Rui
author_role author
author2 Albrecht, Claudia
Gomez Zavaglia, Andrea
Suhm, Martin A.
Fausto, Rui
author2_role author
author
author
author
dc.subject.none.fl_str_mv Pyrazinamide
Infrared Spectroscopy
topic Pyrazinamide
Infrared Spectroscopy
purl_subject.fl_str_mv https://purl.org/becyt/ford/2.11
https://purl.org/becyt/ford/2
dc.description.none.fl_txt_mv A structural and spectroscopic analysis of the anti-tuberculosis drug pyrazinamide (PZA) was carried out. The PZA molecule was predicted theoretically to possess two conformers differing by internal rotation around the C - C(=O) bond, with the E conformer (Cs symmetry point group; N - C - C=O dihedral: 180°) being ca. 30 kJ mol-1 more stable than the Z form (C 1 point group; N - C - C=O dihedral: ca. ± 42°). In consonance with both the large energy difference and low energy barrier between the Z and E conformers, upon isolation in low temperature argon and xenon matrices, only the E form could be observed and characterized spectroscopically. In the argon matrix, this conformer was found to exist in at least three matrix sites, of different stability. In a supersonic jet, besides the monomer (E), the most stable dimer of PZA with two equivalent NH O= hydrogen bonds could also be identified. Its spectrum reveals rapid energy flow out of the excited NH stretching mode mediated by one of the heteroatoms in the ring. Finally, the IR spectra of the amorphous solid resulting from fast cooling of the vapor of the compound (initially in the a crystalline phase) onto the cold substrate of the cryostat (10 K) and of the crystalline phase resulting from warming the amorphous solid were also recorded and interpreted. The obtained crystalline phase was found to be the thermodynamically most stable δ polymorph of PZA.
Fil: Borba, Ana. Universidad de Coimbra; Portugal
Fil: Albrecht, Claudia. Universität Göttingen; Alemania
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. Universidad de Coimbra; Portugal
Fil: Suhm, Martin A.. Universität Göttingen; Alemania
Fil: Fausto, Rui. Universidad de Coimbra; Portugal
description A structural and spectroscopic analysis of the anti-tuberculosis drug pyrazinamide (PZA) was carried out. The PZA molecule was predicted theoretically to possess two conformers differing by internal rotation around the C - C(=O) bond, with the E conformer (Cs symmetry point group; N - C - C=O dihedral: 180°) being ca. 30 kJ mol-1 more stable than the Z form (C 1 point group; N - C - C=O dihedral: ca. ± 42°). In consonance with both the large energy difference and low energy barrier between the Z and E conformers, upon isolation in low temperature argon and xenon matrices, only the E form could be observed and characterized spectroscopically. In the argon matrix, this conformer was found to exist in at least three matrix sites, of different stability. In a supersonic jet, besides the monomer (E), the most stable dimer of PZA with two equivalent NH O= hydrogen bonds could also be identified. Its spectrum reveals rapid energy flow out of the excited NH stretching mode mediated by one of the heteroatoms in the ring. Finally, the IR spectra of the amorphous solid resulting from fast cooling of the vapor of the compound (initially in the a crystalline phase) onto the cold substrate of the cryostat (10 K) and of the crystalline phase resulting from warming the amorphous solid were also recorded and interpreted. The obtained crystalline phase was found to be the thermodynamically most stable δ polymorph of PZA.
publishDate 2010
dc.date.none.fl_str_mv 2010-01
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/11336/131247
Borba, Ana; Albrecht, Claudia; Gomez Zavaglia, Andrea; Suhm, Martin A.; Fausto, Rui; Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase; American Chemical Society; Journal of Physical Chemistry A; 114; 1; 1-2010; 151-161
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/131247
identifier_str_mv Borba, Ana; Albrecht, Claudia; Gomez Zavaglia, Andrea; Suhm, Martin A.; Fausto, Rui; Low Temperature Infrared Spectroscopy Study of Pyrazinamide: from the Isolated Monomer to the Stable Low Temperature Crystalline Phase; American Chemical Society; Journal of Physical Chemistry A; 114; 1; 1-2010; 151-161
1089-5639
1520-5215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp907466h
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp907466h
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
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
_version_ 1842269805832306688
score 13.13397

Publicaciones similares