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Conformational difference between diastereomers of Dnp‐Val‐Aib‐Gly‐Leu‐pNA studied by x‐ray crystal analyses
Author(s) -
Yamada Takashi,
Nakao Masayuki,
Miyazawa Toshifumi,
Kuwata Shigeru,
Sugiura Makiko,
In Yasuko,
Ishida Toshimasa
Publication year - 1993
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.360330509
Subject(s) - chemistry , diastereomer , intramolecular force , hydrogen bond , stereochemistry , chromophore , crystallography , crystal structure , cis–trans isomerism , molecule , photochemistry , organic chemistry
In order to investigate the Conformational change of the α‐aminoisobutyric acid (Aib) containing peptide by the D / L replacement of an amino acid residue, single crystals of two diastereomers, Dnp‐ L ‐Val‐Aib‐Gly‐ L ‐Leu‐pNA ( L ‐ L isomer) and Dnp‐ D ‐Val‐Aib‐Gly‐ L ‐Leu‐pNA ( D ‐ L isomer), were prepared from aqueous methanol solutions as CH 3 OH and CH 3 OH · H 2 O solvates, respectively, and were analyzed by the x‐ray diffraction method. Molecular conformation of L ‐ L isomer adopts consecutive two different types of β‐turns, a type II′ β‐turn bent at Aib‐Gly, and a type III β‐turn bent at Gly‐Leu, stabilized by two intramolecular (Leu) NH … OC (Val) and (pNA) NH … OC(Aib) hydrogen bonds. In contrast, these two intramolecular hydrogen bonds lead the D ‐ L isomer to a distorted 3 10 ‐helix conformation consisting of consecutive two type‐III β‐turn of Aib‐Gly‐Leu sequence. The most significant structural difference between these diastereomers is the mutual orientation between the Dnp and pNA chromophores. While the extensive stacking of both the chromophores is intramolecularly formed for the folded conformation of L ‐ L isomer, they are oriented toward an opposite direction in the open conformation of D ‐ L isomer and are intermolecularly stacked with each other. The large separation between these diastereomers observed in the chromatography is discussed in the relation with their Conformational differences. © 1993 John Wiley & Sons, Inc.