Micron School of Materials Science & Engineering, Boise State University, Boise, Idaho 83725, United States.
Department of Electrical & Computer Engineering, Boise State University, Boise, Idaho 83725, United States.
Biochemistry. 2023 Nov 21;62(22):3234-3244. doi: 10.1021/acs.biochem.3c00471. Epub 2023 Oct 31.
Programmable self-assembly of dyes using DNA templates to promote exciton delocalization in dye aggregates is gaining considerable interest. New methods to improve the rigidity of the DNA scaffold and thus the stability of the molecular dye aggregates to encourage exciton delocalization are desired. In these dye-DNA constructs, one potential way to increase the stability of the aggregates is to create an additional covalent bond via photo-cross-linking reactions between thymines in the DNA scaffold. Specifically, we report an approach to increase the yield of photo-cross-linking reaction between thymines in the core of a DNA Holliday junction while limiting the damage from UV irradiation to DNA. We investigated the effect of the distance between thymines on the photo-cross-linking reaction yields by using linkers with different lengths to tether the dyes to the DNA templates. By comprehensively evaluating the photo-cross-linking reaction yields of dye-DNA aggregates using linkers with different lengths, we conclude that interstrand thymines tend to photo-cross-link more efficiently with short linkers. A higher cross-linking yield was achieved due to the shorter intermolecular distance between thymines influenced by strong dye-dye interactions. Our method establishes the possibility of improving the stability of DNA-scaffolded dye aggregates, thereby expanding their use in exciton-based applications such as light harvesting, nanoscale computing, quantum computing, and optoelectronics.
使用 DNA 模板对染料进行可编程自组装以促进染料聚集体中的激子离域化引起了相当大的兴趣。人们希望找到新的方法来提高 DNA 支架的刚性，从而提高分子染料聚集体的稳定性以促进激子离域化。在这些染料-DNA 结构中，增加聚集体稳定性的一种潜在方法是通过 DNA 支架中的胸腺嘧啶之间的光交联反应来形成额外的共价键。具体来说，我们报告了一种在 DNA 霍利迪结的核心增加胸腺嘧啶之间光交联反应产率的方法，同时限制 DNA 受到的紫外光照射的损伤。我们通过使用不同长度的连接子将染料连接到 DNA 模板上来研究胸腺嘧啶之间的距离对光交联反应产率的影响。通过综合评估具有不同长度的连接子的染料-DNA 聚集体的光交联反应产率，我们得出结论，短连接子使链间胸腺嘧啶更有效地发生光交联。由于受强染料-染料相互作用影响的胸腺嘧啶之间的分子间距离较短，因此实现了更高的交联产率。我们的方法为提高 DNA 支架染料聚集体的稳定性提供了可能性，从而扩展了它们在基于激子的应用中的用途，例如光捕获、纳米计算、量子计算和光电子学。
