Photoswitchable, DNA-Binding Helical Peptides Assembled with Two Independently Designed Sequences for Photoregulation and DNA Recognition

Photoswitchable, DNA-Binding Helical Peptides Assembled with Two Independently Designed Sequences for Photoregulation and DNA Recognition
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DOI:
10.1002/chem.201201431
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发表时间:
2012-08-01
影响因子:
4.3
通讯作者:
Inouye, Masahiko
Inouye, Masahiko
中科院分区:
化学2区
文献类型:
--
作者:
Fujimoto, Kazuhisa;Kajino, Masaoki;Inouye, Masahiko

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二芳基乙烯桥接肽被开发用于光调节生物分子相互作用。这些肽分别在其N-和C-末端由二芳基乙烯桥接和DNA结合区组成。这两个区域可以根据需要独立地设计和组合。肽的α-螺旋度以开/关或关/开的方式受到光调控,并且这种方式依赖于二芳基乙烯桥区域上两个用于交联反应的鸟氨酸(Orn)残基的位置。在开/关方式的情况下,当二芳基乙烯结构在肽上采取开放形式时,肽折叠成稳定的α-螺旋。在UV照射后,二芳基乙烯部分异构化成其封闭形式以使螺旋结构不稳定。石英晶体微天平(QCM)分析表明,开放的异构体与靶DNA强烈相关,相比,封闭的。当存在于DNA复合物中的封闭形式的肽在QCM监测的中间用荧光灯照射时,频率变化(?F)通过二芳基乙烯光异构化而增强。
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 a-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 a-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 (?F) was enhanced by the diarylethene photoisomerization.