Abstract
A sequential polypeptide containing Z-dehydrophenylalanine (ΔZPhe) residues, poly[Lys(Z)-ΔZPhe-Aib], was synthesized to realize a highly stable helical backbone for regularly arranging the β-substituents of dehydroresidues. The polypeptide was prepared by polymerizing the corresponding tripeptide with diphenylphosphoryl azide and fractionated into different molecular weight (MW) species. The polypeptides showed CD profiles with exciton couplets around 276 nm in chloroform, in trimethyl phosphate, and in trifluoroacetic acid, indicating that β-phenyl groups are arranged regularly along the right-handed helical backbone having high conformational stability. Average main-chain conformations in solution of a series of peptides (X-ΔZPhe-Aib)n (n=2, 3, 4, and >4) were estimated by considering conformational energies, and experimental and theoretical CD amplitudes at the same time. Oligopeptides Boc-(Ala-ΔZPhe-Aib)n-OMe (n=2—4) were shown to form a right-handed 310-type helix that contains 3.2—3.3 residues per turn. The polypeptide also formed a right-handed helix but, with increasing MWs, this helix deviated from that of oligopeptides and showed a tendency to form an α-type helix.
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Inai, Y., Ito, T., Hirabayashi, T. et al. Conformation of Sequential Polypeptide Containing Z-Dehydrophenylalanine Residues. Polym J 27, 846–855 (1995). https://doi.org/10.1295/polymj.27.846
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DOI: https://doi.org/10.1295/polymj.27.846