Abstract
Conformation of Asp-containing dipeptides of the general formulae: Ac–Asp–X–NHMe and A–c–X–Asp–NHMe (X = Ser, Lys, Asp, and Tyr) in solution were investigated using 1H and 13C NMR spectroscopy. The dominant formation of a β-turn-like structure was confirmed in the dipeptides, Ac–Ser–Asp–NHMe and Ac–Lys–Asp–NHMe with the deprotonated Asp side chain, from the dependence of the amide proton chemical shifts on temperature, solvent composition, and peptide concentration, and from the backbone dihedral angle φ. The backbone conformations of these dipeptides changed with the deprotonation of Asp. In addition to the intramolecular hydrogen bond of the 4–1 type constituting β-turn structure, other kinds of intramolecular interaction between the carboxylate groups of Asp and side chains of neighboring residues were found in Ac–Ser–Asp–NHMe, Ac–Asp–Ser–NHMe, Ac–Lys–Asp–NHMe by analysis of the side chain rotamer populations, spin-lattice relaxation times, and pKa values. These side chain interactions may possibly contribute to the stabilization of the β-turn-like structure.
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Ishii, H., Inoue, Y. & Chûjô, R. β-Turn-Like Conformation and Side Chain Interactions of Aspartic Acid-Containing Dipeptides. Polym J 16, 9–21 (1984). https://doi.org/10.1295/polymj.16.9
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DOI: https://doi.org/10.1295/polymj.16.9