Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates.
Tuning between Quenching and Energy Transfer in DNA-Templated Heterodimer Aggregates.
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DOI：
10.1021/acs.jpclett.2c00017
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发表时间：
2022-03-31
期刊：
影响因子：
--
通讯作者：
Pensack RD
中科院分区：
文献类型：
--
作者：
Chowdhury AU;Díaz SA;Huff JS;Barclay MS;Chiriboga M;Ellis GA;Mathur D;Patten LK;Sup A;Hallstrom N;Cunningham PD;Lee J;Davis PH;Turner DB;Yurke B;Knowlton WB;Medintz IL;Melinger JS;Pensack RD
通过电子能量转移在空间上传播的分子激子是许多应用的核心，包括光收集、有机光电子学和纳米级计算；它们也可能有利于光热治疗和光声成像等应用，通过快速激发态猝灭局部产生热量。在这里，我们展示了如何通过改变异质二聚体在DNA模板上的空间结构来调节同一对花青素染料的能量转移和猝灭。我们使用DNA Holliday连接组装Cy5和Cy5.5的“横向”和“相邻”异源二聚体。我们发现横向的异源二聚体表现出与激态相互作用染料和荧光猝灭一致的光学性质，而相邻的异源二聚体表现出与非激态相互作用染料一致的光学性质和不相称的大Cy5.5发射，表明染料之间的能量转移。我们使用瞬态吸收光谱显示，横向异二聚体的猝灭是通过快速非辐射衰变到基态（~ 31 ps）发生的，而在相邻的异二聚体中，从Cy5到Cy5.5的快速能量转移（~ 420 fs）之后是Cy5.5激发态弛豫（~ 700 ps）。访问如此截然不同的光物理，可以根据不同的目标应用需求进行调整，突出了DNA作为染料聚集模板的实用性。
Molecular excitons, which propagate spatially via electronic energy transfer, are central to numerous applications including light harvesting, organic optoelectronics, and nanoscale computing; they may also benefit applications such as photothermal therapy and photoacoustic imaging through the local generation of heat via rapid excited-state quenching. Here we show how to tune between energy transfer and quenching for heterodimers of the same pair of cyanine dyes by altering their spatial configuration on a DNA template. We assemble “transverse” and “adjacent” heterodimers of Cy5 and Cy5.5 using DNA Holliday junctions. We find that the transverse heterodimers exhibit optical properties consistent with excitonically interacting dyes and fluorescence quenching, while the adjacent heterodimers exhibit optical properties consistent with nonexcitonically interacting dyes and disproportionately large Cy5.5 emission, suggestive of energy transfer between dyes. We use transient absorption spectroscopy to show that quenching in the transverse heterodimer occurs via rapid nonradiative decay to the ground state (∼31 ps) and that in the adjacent heterodimer rapid energy transfer from Cy5 to Cy5.5 (∼420 fs) is followed by Cy5.5 excited-state relaxation (∼700 ps). Accessing such drastically different photophysics, which may be tuned on demand for different target applications, highlights the utility of DNA as a template for dye aggregation.
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