Fujimoto Jun, Bando Toshikazu, Minoshima Masafumi, Kashiwazaki Gengo, Nishijima Shigeki, Shinohara Ken-ichi, Sugiyama Hiroshi
Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Sakyo, Kyoto 606-8502, Japan.
Bioorg Med Chem. 2008 Nov 15;16(22):9741-4. doi: 10.1016/j.bmc.2008.09.073. Epub 2008 Oct 7.
Perylene-conjugated pyrrole (Py)-polyamide 2 was designed and synthesized using the Fmoc solid-phase synthesis and a subsequent Sonogashira coupling reaction with 3-bromoperylene. Interestingly, conjugate 2 did not luminesce in water at 313 nm irradiation but was turned on in the presence of target double-stranded (ds) DNA, and showed strong emission with increasing DNA concentration, in particularly, by the binding to the target telomere sequences through heterodimer formation with partner 3. Importantly, the excitation spectrum of 2 clearly indicates that the Py and Imidazole (Im) moieties in the polyamide effectively sensitize the perylene moiety to give rise to fluorescence emission. Energy transfer would occur from the Py moiety to the perylene. Thus, screening of perylene-conjugates will allow us to develop a novel "molecular light switch" with sequence-specificity.
使用Fmoc固相合成法以及随后与3-溴苝进行的Sonogashira偶联反应，设计并合成了苝共轭吡咯（Py）-聚酰胺2。有趣的是，共轭物2在313 nm光照下于水中不发光，但在目标双链（ds）DNA存在时被开启，并随着DNA浓度的增加而显示出强烈的发射，特别是通过与伴侣3形成异二聚体与目标端粒序列结合。重要的是，2的激发光谱清楚地表明聚酰胺中的Py和咪唑（Im）部分有效地敏化了苝部分以产生荧光发射。能量转移将从Py部分发生到苝。因此，筛选苝共轭物将使我们能够开发一种具有序列特异性的新型“分子光开关”。
