title: Influence of the O-phosphorylation of serine, threonine and tyrosine in proteins on the amidic ¹⁵N chemical shielding anisotropy tensors.
abstract: Density functional theory was employed to study the influence of O-phosphorylation of serine, threonine, and tyrosine on the amidic (15)N chemical shielding anisotropy (CSA) tensor in the context of the complex chemical environments of protein structures. Our results indicate that the amidic (15)N CSA tensor has sensitive responses to the introduction of the phosphate group and the phosphorylation-promoted rearrangement of solvent molecules and hydrogen bonding networks in the vicinity of the phosphorylated site. Yet, the calculated (15)N CSA tensors in phosphorylated model peptides were in range of values experimentally observed for non-phosphorylated proteins. The extent of the phosphorylation induced changes suggests that the amidic (15)N CSA tensor in phosphorylated proteins could be reasonably well approximated with averaged CSA tensor values experimentally determined for non-phosphorylated amino acids in practical NMR applications, where chemical surrounding of the phosphorylated site is not known a priori in majority of cases. Our calculations provide estimates of relative errors to be associated with the averaged CSA tensor values in interpretations of NMR data from phosphorylated proteins.
authors.affiliation: Biology Centre, Academy of Science of the Czech Republic and University of South Bohemia, Branišovská 31, 370 05 České Budějovice, Czech Republic.
authors.forename: Jiří
authors.initials: J
authors.lastname: Emmer
authors.forename: Andrea
authors.initials: A
authors.lastname: Vavrinská
authors.forename: Vladimír
authors.initials: V
authors.lastname: Sychrovský
authors.forename: Ladislav
authors.initials: L
authors.lastname: Benda
authors.forename: Zdeněk
authors.initials: Z
authors.lastname: Kříž
authors.forename: Jaroslav
authors.initials: J
authors.lastname: Koča
authors.forename: Rolf
authors.initials: R
authors.lastname: Boelens
authors.forename: Vladimír
authors.initials: V
authors.lastname: Sklenář
authors.forename: Lukáš
authors.initials: L
authors.lastname: Trantírek
mesh_terms: D016880:Anisotropy; D009587:Nitrogen Isotopes / Q000737:chemistry; D019906:Nuclear Magnetic Resonance, Biomolecular; D010455:Peptides / Q000737:chemistry; D010710:Phosphates / Q000737:chemistry; D010766:Phosphorylation; D011506:Proteins / Q000737:chemistry*; D012694:Serine / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013912:Threonine / Q000737:chemistry*; D014443:Tyrosine / Q000737:chemistry*
chemical_list: D009587:Nitrogen Isotopes; D010455:Peptides; D010710:Phosphates; D011506:Proteins; D012997:Solvents; D013912:Threonine; D014443:Tyrosine; D012694:Serine