title: Position dependence of the 13C chemical shifts of alpha-helical model peptides. Fingerprint of the 20 naturally occurring amino acids.
abstract: The position dependence of the (13)C chemical shifts was investigated at the density functional level for alpha-helical model peptides represented by the sequence Ac-(Ala)(i)-X-(Ala)(j)-NH(2), where X represents any of the 20 naturally occurring amino acids, with 0 < or = i < or = 8 and i + j = 8. Adoption of the locally dense basis approach for the quantum chemical calculations enabled us to reduce the length of the chemical-shift calculations while maintaining good accuracy of the results. For the 20 naturally occurring amino acids in alpha-helices, there is (1) significant variability of the computed (13)C shielding as a function of both the guest residue (X) and the position along the sequence; for example, at the N terminus, the (13)C(alpha) and (13)C(beta) shieldings exhibit a uniform pattern of variation with respect to both the central or the C-terminal positions; (2) good agreement between computed and observed (13)C(alpha) and (13)C(beta) chemical shifts in the interior of the helix, with correlation coefficients of 0.98 and 0.99, respectively; for (13)C(alpha) chemical shifts, computed in the middle of the helix, only five residues, namely Asn, Asp, Ser, Thr, and Leu, exhibit chemical shifts beyond the observed standard deviation; and (3) better agreement for four of these residues (Asn, Asp, Ser, and Thr) only for the computed values of the (13)C(alpha) chemical shifts at the N terminus. The results indicate that (13)C(beta), but not (13)C(beta), chemical shifts are sensitive enough to reflect the propensities of some amino acids for specific positions within an alpha-helix, relative to the N and C termini of peptides and proteins.
authors.affiliation: Baker Laboratory of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853-1301, USA.
authors.forename: Jorge A
authors.initials: JA
authors.lastname: Vila
authors.forename: Héctor A
authors.initials: HA
authors.lastname: Baldoni
authors.forename: Harold A
authors.initials: HA
authors.lastname: Scheraga
mesh_terms: D000595:Amino Acid Sequence; D000596:Amino Acids; D002247:Carbon Isotopes; D008962:Models, Theoretical; D019906:Nuclear Magnetic Resonance, Biomolecular; D010455:Peptides / Q000737:chemistry*; D017433:Protein Structure, Secondary
chemical_list: D000596:Amino Acids; D002247:Carbon Isotopes; D010455:Peptides