Precision Measurements of Deuterium Isotope Effects on the Chemical Shifts of Backbone Nuclei in Proteins: Correlations with Secondary Structure

Precision NMR measurements of deuterium isotope effects on the chemical shifts of backbone nuclei in proteins (15N, 13CO, 13Cα, and 1HN) arising from 1H-to-2H substitutions at aliphatic carbon sites. Isolation of molecular species with a defined protonation/deuteration pattern at carbon-α/β position...

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Bibliographic Details
Published in:The journal of physical chemistry. B 2012-06, Vol.116 (25), p.7436-7448
Main Authors: Sun, Hechao, Tugarinov, Vitali
Format: Article
Language:English
Subjects:
Amides - chemistry
Backbone
Carbon - chemistry
Deuteration
Deuterium
Deuterium - chemistry
Humans
Isotope effect
Isotopes
Models, Molecular
Nitrogen - chemistry
Nuclear magnetic resonance
Nuclear Magnetic Resonance, Biomolecular - methods
Nuclei
Protein Structure, Secondary
Proteins
Ubiquitin - chemistry
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Summary:Precision NMR measurements of deuterium isotope effects on the chemical shifts of backbone nuclei in proteins (15N, 13CO, 13Cα, and 1HN) arising from 1H-to-2H substitutions at aliphatic carbon sites. Isolation of molecular species with a defined protonation/deuteration pattern at carbon-α/β positions allows distinguishing and accurately quantifying different isotope effects within the protein backbone. The isotope shifts measured in the partially deuterated protein ubiquitin are interpreted in terms of backbone geometry via empirical relationships describing the dependence of isotope shifts on (φ; ψ) backbone dihedral angles. Because of their relatively large magnitude and clear dependence on the protein secondary structure, the two- and three-bond backbone amide 15N isotope shifts, 2ΔN(Cα,iD) and 3ΔN(Cα,i‑1D), can find utility for NMR structural refinement of small-to-medium size proteins.
ISSN:1520-6106
1520-5207
DOI:10.1021/jp304300n