Bright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns.
Bright G-Quadruplex Nanostructures Functionalized with Porphyrin Lanterns.
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DOI：
10.1021/jacs.9b03250
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发表时间：
2019-08-14
影响因子：
15
通讯作者：
Jayawickramarajah J
中科院分区：
文献类型：
--
作者：
Pathak P;Yao W;Hook KD;Vik R;Winnerdy FR;Brown JQ;Gibb BC;Pursell ZF;Phan AT;Jayawickramarajah J
大量紧密排列在纳米支架上的发色团的复杂排列可以导致关键的光子应用，从光波导和天线到信号增强型荧光传感器。在这方面，将染料附加的DNA序列自组装成程序化的光子结构是很有前途的。然而，染料的密集堆积不仅会导致dna组装受损(导致结构和沉淀物定义不清)，还会导致本质上的非荧光系统(由于π-π聚集)。在这里，我们介绍了一种两步法，即首先将大的卟啉染料连接到短的G-四链体形成序列上，然后与全O-甲基化的β-环糊精(PMβCD)帽反应，形成超分子合成子，由于水中分子内的主-客体相互作用，使卟啉荧光固定在掩蔽的卟啉灯笼(PL)状态。然后，PL-DNA序列可以自组装成环状结构或史无前例的G-线，与数百种卟啉染料捆绑在一起。重要的是，尽管荧光单元排列紧密(~2 nm)，但这些染料表现为明亮的发色团(比没有PMβCD掩模的类似物亮180倍)。由于其他自组装支架、染料和主体分子可以在这种模块化方法中使用，因此这篇手稿为含有密集染料的明亮纳米材料的自下而上的水溶液自组装制定了一般策略。
The intricate arrangement of numerous and closely placed chromophores on nanoscale scaffolds can lead to key photonic applications ranging from optical waveguides and antennas to signal-enhanced fluorescent sensors. In this regard, the self-assembly of dye-appended DNA sequences into programmed photonic architectures is promising. However, the dense-packing of dyes can result in not only compromised DNA assembly (leading to ill-defined structures and precipitates) but also to essentially non-fluorescent systems (due to π-π aggregation). Here, we introduce a two-step “tether and mask” strategy wherein large porphyrin dyes are first attached to short G-quadruplex forming sequences and then reacted with per-O-methylated β-cyclodextrin (PMβCD) caps, to form supramolecular synthons featuring the porphyrin fluor fixed into a masked porphyrin lantern (PL) state, due to intramolecular host-guest interactions in water. The PL-DNA sequences can then be self-assembled into cyclic architectures or unprecedented G-wires tethered with hundreds of porphyrin dyes. Importantly, despite the closely arrayed PL units (~2 nm), the dyes behave as bright chromophores (up to 180-fold brighter than the analogues lacking the PMβCD masks). Since other self-assembling scaffolds, dyes, and host molecules can be used in this modular approach, this manuscript lays a general strategy for the bottom-up aqueous self-assembly of bright nanomaterials containing densely packed dyes.
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影响因子：
15
作者：
Balaz, M;Holmes, AE;Proni, G
通讯作者：
Proni, G
影响因子：
2.1
作者：
Hocquelet, C.;Blu, J.;Mauclaire, L.
通讯作者：
Mauclaire, L.
影响因子：
4.9
作者：
Li, Shaoguang;Langenegger, Simon M.;Haener, Robert
通讯作者：
Haener, Robert
影响因子：
4.3
作者：
Hong, Yuning;Haeussler, Matthias;Tang, Ben Zhong
通讯作者：
Tang, Ben Zhong
影响因子：
16.6
作者：
Balaz, Milan;Li, Benjamin C.;Berova, Nina
通讯作者：
Berova, Nina