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dc.contributor.author
Vila, Jorge Alberto
dc.contributor.author
Scheraga, Harold A.
dc.date.available
2018-11-26T22:26:03Z
dc.date.issued
2017-04
dc.identifier.citation
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
dc.identifier.issn
0022-2860
dc.identifier.uri
http://hdl.handle.net/11336/65246
dc.description.abstract
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.
dc.format
application/pdf
dc.language.iso
eng
dc.publisher
Elsevier Science
dc.rights
info:eu-repo/semantics/openAccess
dc.rights.uri
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.subject
High-Ph Limiting Values
dc.subject
Histidine Tautomers
dc.subject
One-Bond Spin-Spin Coupling Constant
dc.subject
Protonated Form of His
dc.subject
Solvent Effects
dc.subject
Sscc
dc.subject.classification
Física Atómica, Molecular y Química
dc.subject.classification
Ciencias Físicas
dc.subject.classification
CIENCIAS NATURALES Y EXACTAS
dc.title
Limiting values of the one-bond C[sbnd]H spin-spin coupling constants of the imidazole ring of histidine at high-pH
dc.type
info:eu-repo/semantics/article
dc.type
info:ar-repo/semantics/artículo
dc.type
info:eu-repo/semantics/publishedVersion
dc.date.updated
2018-10-23T17:38:41Z
dc.journal.volume
1134
dc.journal.pagination
576-581
dc.journal.pais
Países Bajos
dc.journal.ciudad
Amsterdam
dc.description.fil
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
dc.description.fil
Fil: Scheraga, Harold A.. Cornell University; Estados Unidos
dc.journal.title
Journal of Molecular Structure
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/doi/http://dx.doi.org/10.1016/j.molstruc.2017.01.022
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286017300236
dc.relation.alternativeid
info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5596661/
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