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Photoswitchable, DNA‐Binding Helical Peptides Assembled with Two Independently Designed Sequences for Photoregulation and DNA Recognition
Author(s) -
Fujimoto Kazuhisa,
Kajino Masaoki,
Sakaguchi Ikumi,
Inouye Masahiko
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201201431
Subject(s) - diarylethene , photoisomerization , chemistry , peptide , dna , photochromism , moiety , fluorescence , photoswitch , stereochemistry , helix (gastropod) , photochemistry , combinatorial chemistry , biophysics , crystallography , biochemistry , isomerization , biology , catalysis , optics , ecology , physics , snail
Diarylethene‐bridged peptides were developed to photoregulate biomolecular interactions. The peptides are made up of diarylethene‐bridged and DNA‐binding regions at their N‐ and C termini, respectively. The two regions could be independently designed and combined as desired. The α‐helicities of the peptides were photoregulated in on/off or off/on manners, and the manner depended on the positions of two ornithine (Orn) residues for cross‐linking reaction at the diarylethene‐bridged region. In the case of the on/off manner, when the diarylethene structure adopted the open form on the peptides, the peptides folded into stable α‐helices. Upon UV irradiation, the diarylethene moiety isomerized to its closed form to destabilize the helical structures. Quartz crystal microbalance (QCM) analysis showed that the open isomer strongly associated with a target DNA, as compared with the closed one. When the closed‐form peptide existing in the DNA complex was irradiated with a fluorescent lamp in the middle of the QCM monitoring, the frequency change (Δ F ) was enhanced by the diarylethene photoisomerization.