Concurrent formation of H- and J-aggregates of dyes with chiralities individually determined by G-quadruplex handedness.
Concurrent formation of H- and J-aggregates of dyes with chiralities individually determined by G-quadruplex handedness.
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DOI：
10.1016/j.saa.2020.119270
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发表时间：
2020-12
期刊：
影响因子：
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通讯作者：
Chenxiao Yan;Qingqing Zhang;Heng Gao;Xiong Zheng;Tong Yang;Guoxiang Zheng;Xiaoshun Zhou;Yong Shao
中科院分区：
文献类型：
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作者：
Chenxiao Yan;Qingqing Zhang;Heng Gao;Xiong Zheng;Tong Yang;Guoxiang Zheng;Xiaoshun Zhou;Yong Shao
DNA模板染料组件为调节分子聚集体的光学性质铺平了一条简单的途径。G-四链体(G4S)为染料组件提供了多种DNA平台，因为它们的折叠可以很容易地通过阳离子和序列来调节。在这项工作中，我们发现G4手性可以用来控制3，3‘-二乙基硫代碳菁(DiSC2(3))染料的聚集手性。左旋和右旋G4S可以模板DiSC2(3)的J-和H-聚集体的同时形成，并出现特征吸收光谱。然而，DiSC2(3)的手性J-聚集体只能在左手G4S上形成，而手性H-聚集体只能在右手G4S上生长，这从具有特征分裂带的诱导圆二色谱(ICD)中得到了证实。此外，这些G4S即使在几十纳米级也能有效地产生这些手性聚集体，显示出G4S在创建这些光学活性染料组件方面的高灵敏度。聚集体的可能生长部位由序列长度相关的组装提出。我们的工作将为通过G4手性控制染料聚集体的手性组装提供一种新的方法。
DNA templated dye assemblies pave an easy way to regulate the optical properties of molecular aggregates. G-quadruplexes (G4s) provide versatile DNA platforms for the dye assemblies since their foldings can be easily tuned by cation ions and sequences. In this work, we found that the G4 handedness can be used to control the aggregate chirality of a dye of 3,3′-diethylthiacarbocyanine (DiSC2(3)). The left-handed and right-handed G4s can template the concurrent formation of the J- and H-aggregates of DiSC2(3) with emergence of the featured absorption spectra. However, the chiral J-aggregate of DiSC2(3) can be formed only on the left-handed G4s, while the chiral H-aggregate is otherwise grown only on the right-handed G4s, as confirmed by the induced circular dichroism (ICD) spectra with the characteristic splitting bands. Additionally, these G4s even at tens of nM level are efficient to produce these chiral aggregates, demonstrating the high sensitivity of G4s in creating these optically active dye assemblies. The possible growth sites of the aggregates are proposed by the sequence length-dependent assemblies. Our work will provide a new way to control the chiral assemblies of dye aggregates via the G4 handedness.