Structural and optical variation of pseudoisocyanine aggregates nucleated on DNA substrates.
Structural and optical variation of pseudoisocyanine aggregates nucleated on DNA substrates.
复制标题
DOI：
10.1088/2050-6120/acb2b4
复制
发表时间：
2023-01-31
影响因子：
3.2
通讯作者：
Díaz SA
中科院分区：
文献类型：
--
作者：
Chiriboga M;Green CM;Mathur D;Hastman DA;Melinger JS;Veneziano R;Medintz IL;Díaz SA
相干耦合的假异氰（PIC）染料聚集体已经证明了使电子激发离域并最终以比其中激发被隔离到单个发色团的类似设计高得多的效率迁移激子的能力。在这里，我们报告了一种新型的PIC聚集体的初步证据，通过DNA寡核苷酸上的异质成核形成，显示与以前报道的聚集体显着不同的物理性质。这种新的聚集体，我们称之为超聚集体（SA），由于需要提高染料过量形成它，是明确区分从以前报道的聚集体的光谱和生物物理特性。在发射光谱中，SA表现出峰变窄，并且在某些情况下，显着的量子产率变化，指示花青染料中的较强耦合。SA的进一步特征在于圆二色性和原子力显微镜观察独特的功能取决于DNA基板。然后通过将AlexaFluor™ 647（AF）染料作为能量转移受体整合到系统中，我们观察到使用不同DNA的混合能量转移特性。例如，用刚性DNA双交叉瓦片（DX瓦片）衬底形成的SA导致AF发射敏化。而与更柔性的非DX-tile DNA（即双链体和单链DNA）形成的SA导致AF发射淬灭。这些组合的特征强烈暗示，DNA为基础的PIC聚集体的性质可以通过简单的修改DNA基板的序列和几何形状进行控制。最终，我们的目标是为未来的设备原型设计提供合理的设计原则。例如，该研究的一个关键结论是，与柔性DNA基底相比，刚性基底观察到的高吸收横截面和有效的能量转移是更好的光子天线。
Coherently coupled pseudoisocyanine (PIC) dye aggregates have demonstrated the ability to delocalize electronic excitations and ultimately migrate excitons with much higher efficiency than similar designs where excitations are isolated to individual chromophores. Here, we report initial evidence of a new type of PIC aggregate, formed through heterogeneous nucleation on DNA oligonucleotides, displaying photophysical properties that differ significantly from previously reported aggregates. This new aggregate, which we call the super aggregate (SA) due to the need for elevated dye excess to form it, is clearly differentiated from previously reported aggregates by spectroscopic and biophysical characterization. In emission spectra, the SA exhibits peak narrowing and, in some cases, significant quantum yield variation, indicative of stronger coupling in cyanine dyes. The SA was further characterized with circular dichroism and atomic force microscopy observing unique features depending on the DNA substrate. Then by integrating an AlexaFluor™ 647 (AF) dye as an energy transfer acceptor into the system, we observed mixed energy transfer characteristics using the different DNA. For example, SA formed with a rigid DNA double crossover tile (DX-tile) substrate resulted in AF emission sensitization. While SA formed with more flexible non-DX-tile DNA (i.e. duplex and single strand DNA) resulted in AF emission quenching. These combined characterizations strongly imply that DNA-based PIC aggregate properties can be controlled through simple modifications to the DNA substrate’s sequence and geometry. Ultimately, we aim to inform rational design principles for future device prototyping. For example, one key conclusion of the study is that the high absorbance cross-section and efficient energy transfer observed with rigid substrates made for better photonic antennae, compared to flexible DNA substrates.
登录
查看更多内容
DOI：
10.1021/acs.jpcb.1c09048
发表时间：
2022-01-13
期刊：
The journal of physical chemistry. B
影响因子：
--
作者：
Chiriboga M;Diaz SA;Mathur D;Hastman DA;Melinger JS;Veneziano R;Medintz IL
通讯作者：
Medintz IL
影响因子：
5.7
作者：
Hart, Stephanie M.;Wang, Xiao;Schlau-Cohen, Gabriela S.
通讯作者：
Schlau-Cohen, Gabriela S.
影响因子：
4.4
作者：
Bricker, William P.;Banal, James L.;Bathe, Mark
通讯作者：
Bathe, Mark
影响因子：
2.4
作者：
FORSTER, T
通讯作者：
FORSTER, T
影响因子：
10.8
作者：
Fofang, Nche T.;Park, Tae-Ho;Halas, Naomi J.
通讯作者：
Halas, Naomi J.