在偶氮苯上引入甲基以实现对杂交的有效光调控和抑制热异构化。

Incorporation of methyl group on azobenzene for the effective photo-regulation of hybridization and suppression of thermal isomerization.

作者信息

Nishioka Hidenori, Kashida Hiromu, Komiyama Makoto, Liang Xingguo, Asanuma Hiroyuki

机构信息

Department of Molecular Design and Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan.

出版信息

Nucleic Acids Symp Ser (Oxf). 2006(50):85-6. doi: 10.1093/nass/nrl042.

DOI:10.1093/nass/nrl042

PMID:17150829

Abstract

We have synthesized azobenzene-tethered DNAs and have successfully photo-regulated various DNA functions. In the present study, we synthesized azobenzenes substituted with methyl group for still more effective photo-regulation of DNA hybridization. In trans-form, mono substituted azobenzene at ortho position stabilized the DNA duplex more efficiently than the other mono-substituted ones. In contrast, melting temperature (T(m)) for 2-methylazobenzene was lower in cis-form. As a result, change of T(m) (DeltaT(m)) induced by trans-cis isomerization became larger than that of unmodified azobenzene. Furthermore, di-substituted azobenzene at both ortho positions exhibited even larger DeltaT(m). Quite interestingly, thermal cis-to-trans isomerization of this azobenzene was about 10-fold slower than that of unmodified one. Thus, introduction of methyl group at 2, 6 positions raised both photo-regulatory activity and thermal stability of cis-form.

摘要

我们合成了偶氮苯连接的DNA，并成功地对各种DNA功能进行了光调控。在本研究中，我们合成了用甲基取代的偶氮苯，以实现对DNA杂交更有效的光调控。在反式结构中，邻位单取代偶氮苯比其他单取代偶氮苯更有效地稳定DNA双链体。相比之下，2-甲基偶氮苯的顺式结构的解链温度（T(m)）较低。因此，反-顺异构化诱导的T(m)变化（ΔT(m)）比未修饰的偶氮苯更大。此外，两个邻位均为双取代的偶氮苯表现出更大的ΔT(m)。非常有趣的是，这种偶氮苯的热顺-反异构化比未修饰的偶氮苯慢约10倍。因此，在2,6位引入甲基提高了顺式结构的光调控活性和热稳定性。