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Chiral interaction in Gly‐capped N‐terminal motif of 3 10 ‐helix and domino‐type induction in helix sense
Author(s) -
Ousaka Naoki,
Inai Yoshihito,
Okabe Takahiro
Publication year - 2006
Publication title -
biopolymers
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.556
H-Index - 125
eISSN - 1097-0282
pISSN - 0006-3525
DOI - 10.1002/bip.20557
Subject(s) - chemistry , helix (gastropod) , stereochemistry , peptide , circular dichroism , asymmetric induction , amino acid , molecule , chirality (physics) , peptide conformation , triple helix , crystallography , enantioselective synthesis , physics , organic chemistry , biochemistry , catalysis , ecology , nambu–jona lasinio model , chiral symmetry breaking , quantum mechanics , quark , snail , biology
Chiral interaction of helical peptide with chiral molecule, and concomitant induction in its helix sense have been demonstrated in optically inactive nonapeptide ( 1 ) possessing Gly at its N‐terminus: H–Gly–(Δ Z Phe–Aib) 4 –OCH 3 ( 1 : Δ Z Phe = Z‐dehydrophenylalanine; Aib = α‐aminoisobutyric acid). Spectroscopic measurements [mainly nuclear magnetic resonance (NMR) and circular diochroism (CD)] as well as theoretical simulation have been carried out for that purpose. Peptide 1 in the 3 10 ‐helix tends to adopt preferentially a right‐handed screw sense by chiral Boc‐ L ‐amino acid (Boc: t ‐butoxycarbonyl). Induction in the helix sense through the noncovalent chiral domino effect should be derived primarily from the complex supported by the three‐point coordination on the N‐terminal sequence. Thus the 3 10 ‐helical terminus consisting of only α‐amino acid residues enables chiral recognition of the Boc‐amino acid molecule, leading to modulation of the original chain asymmetry. Dynamics in the helix‐sense induction also have been discussed on the basis of a low‐temperature NMR study. Furthermore, the inversion of induced helix sense has been achieved through solvent effects. © 2006 Wiley Periodicals, Inc. Biopolymers 83:337–351, 2006 This article was originally published online as an accepted preprint. The “Published Online” date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com