Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH

Assessment of the relative amounts of the forms of the imidazole ring of Histidine (His), namely the protonated (H+) and the tautomeric Nε2-H and Nδ1-H forms, respectively, is a challenging task in NMR spectroscopy. Indeed, their determination by direct observation of the 15N and 13C chemical shifts...

Descripción completa

Detalles Bibliográficos
Autores: Vila, Jorge Alberto, Scheraga, Harold A.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2017
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/65246
Acceso en línea:http://hdl.handle.net/11336/65246
Access Level:acceso abierto
Palabra clave:High-Ph Limiting Values
Histidine Tautomers
One-Bond Spin-Spin Coupling Constant
Protonated Form of His
Solvent Effects
Sscc
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
id AR_210f8167fdf2d41bb3e9cb87b852ee7a
oai_identifier_str oai:ri.conicet.gov.ar:11336/65246
network_acronym_str AR
network_name_str Argentina
repository_id_str
spelling Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pHVila, Jorge AlbertoScheraga, Harold A.High-Ph Limiting ValuesHistidine TautomersOne-Bond Spin-Spin Coupling ConstantProtonated Form of HisSolvent EffectsSscchttps://purl.org/becyt/ford/1.3https://purl.org/becyt/ford/1Assessment of the relative amounts of the forms of the imidazole ring of Histidine (His), namely the protonated (H+) and the tautomeric Nε2-H and Nδ1-H forms, respectively, is a challenging task in NMR spectroscopy. Indeed, their determination by direct observation of the 15N and 13C chemical shifts or the one-bond C[sbnd]H, 1JCH, Spin-Spin Coupling Constants (SSCC) requires knowledge of the “canonical” limiting values of these forms in which each one is present to the extent of 100%. In particular, at high-pH, an accurate determination of these “canonical” limiting values, at which the tautomeric forms of His coexist, is an elusive problem in NMR spectroscopy. Among different NMR-based approaches to treat this problem, we focus here on the computation, at the DFT level of theory, of the high-pH limiting value for the 1JCH SSCC of the imidazole ring of His. Solvent effects were considered by using the polarizable continuum model approach. The results of this computation suggest, first, that the value of 1JCε1H = 205 ± 1.0 Hz should be adopted as the canonical high-pH limiting value for this SSCC; second, the variation of 1JCε1H SSCC during tautomeric changes is minor, i.e., within ±1 Hz; and, finally, the value of 1JCδ2H SSCC upon tautomeric changes is large (15 Hz) indicating that, at high-pH or for non-protonated His at any pH, the tautomeric fractions of the imidazole ring of His can be predicted accurately as a function of the observed value of 1JCδ2H SSCC.Fil: Vila, Jorge Alberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - San Luis. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi". Universidad Nacional de San Luis. Facultad de Ciencias Físico, Matemáticas y Naturales. Instituto de Matemática Aplicada de San Luis "Prof. Ezio Marchi"; ArgentinaFil: Scheraga, Harold A.. Cornell University; Estados UnidosElsevier Science2017-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/65246Vila, Jorge Alberto; Scheraga, Harold A.; Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH; Elsevier Science; Journal of Molecular Structure; 1134; 4-2017; 576-5810022-2860CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2017.01.022info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286017300236info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5596661/info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2024-05-08T13:42:03Zoai:ri.conicet.gov.ar:11336/65246instacron: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:34982024-05-08 13:42:03.505CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
title Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
spellingShingle Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
Vila, Jorge Alberto
High-Ph Limiting Values
Histidine Tautomers
One-Bond Spin-Spin Coupling Constant
Protonated Form of His
Solvent Effects
Sscc
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
title_short Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
title_full Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
title_fullStr Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
title_full_unstemmed Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
title_sort Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
dc.creator.none.fl_str_mv Vila, Jorge Alberto
Scheraga, Harold A.
author Vila, Jorge Alberto
author_facet Vila, Jorge Alberto
Scheraga, Harold A.
author_role author
author2 Scheraga, Harold A.
author2_role author
dc.subject.none.fl_str_mv High-Ph Limiting Values
Histidine Tautomers
One-Bond Spin-Spin Coupling Constant
Protonated Form of His
Solvent Effects
Sscc
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
topic High-Ph Limiting Values
Histidine Tautomers
One-Bond Spin-Spin Coupling Constant
Protonated Form of His
Solvent Effects
Sscc
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
description Assessment of the relative amounts of the forms of the imidazole ring of Histidine (His), namely the protonated (H+) and the tautomeric Nε2-H and Nδ1-H forms, respectively, is a challenging task in NMR spectroscopy. Indeed, their determination by direct observation of the 15N and 13C chemical shifts or the one-bond C[sbnd]H, 1JCH, Spin-Spin Coupling Constants (SSCC) requires knowledge of the “canonical” limiting values of these forms in which each one is present to the extent of 100%. In particular, at high-pH, an accurate determination of these “canonical” limiting values, at which the tautomeric forms of His coexist, is an elusive problem in NMR spectroscopy. Among different NMR-based approaches to treat this problem, we focus here on the computation, at the DFT level of theory, of the high-pH limiting value for the 1JCH SSCC of the imidazole ring of His. Solvent effects were considered by using the polarizable continuum model approach. The results of this computation suggest, first, that the value of 1JCε1H = 205 ± 1.0 Hz should be adopted as the canonical high-pH limiting value for this SSCC; second, the variation of 1JCε1H SSCC during tautomeric changes is minor, i.e., within ±1 Hz; and, finally, the value of 1JCδ2H SSCC upon tautomeric changes is large (15 Hz) indicating that, at high-pH or for non-protonated His at any pH, the tautomeric fractions of the imidazole ring of His can be predicted accurately as a function of the observed value of 1JCδ2H SSCC.
publishDate 2017
dc.date.none.fl_str_mv 2017-04
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/11336/65246
Vila, Jorge Alberto; Scheraga, Harold A.; Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH; Elsevier Science; Journal of Molecular Structure; 1134; 4-2017; 576-581
0022-2860
CONICET Digital
CONICET
url http://hdl.handle.net/11336/65246
identifier_str_mv Vila, Jorge Alberto; Scheraga, Harold A.; Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH; Elsevier Science; Journal of Molecular Structure; 1134; 4-2017; 576-581
0022-2860
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2017.01.022
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286017300236
info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5596661/
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier Science
publisher.none.fl_str_mv Elsevier Science
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
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_ 1799195039637700608
score 15,811543

Similares en LA Referencia