Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
- Autores
- Vila, Jorge Alberto; Scheraga, Harold A.
- Año de publicación
- 2017
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- 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.
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"; Argentina
Fil: Scheraga, Harold A.. Cornell University; Estados Unidos - Materia
-
High-Ph Limiting Values
Histidine Tautomers
One-Bond Spin-Spin Coupling Constant
Protonated Form of His
Solvent Effects
Sscc - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
- Repositorio
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/65246
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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 Técnicas2025-09-29T09:44:25Zoai: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:34982025-09-29 09:44:25.831CONICET 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 |
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 |
topic |
High-Ph Limiting Values Histidine Tautomers One-Bond Spin-Spin Coupling Constant Protonated Form of His Solvent Effects Sscc |
purl_subject.fl_str_mv |
https://purl.org/becyt/ford/1.3 https://purl.org/becyt/ford/1 |
dc.description.none.fl_txt_mv |
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. 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"; Argentina Fil: Scheraga, Harold A.. Cornell University; Estados Unidos |
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 |
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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1844613398107521024 |
score |
13.070432 |