Department of Regulatory Bioorganic Chemistry, The Institute of Scientific and Industrial Research, Osaka University, Ibaraki, Osaka 567-0047, Japan.
Chem Soc Rev. 2011 Dec;40(12):5718-29. doi: 10.1039/c1cs15062f. Epub 2011 Jun 20.
Hybridization of DNA is one of the most intriguing events in molecular recognition and is essential for living matter to inherit life beyond generations. In addition to the function of DNA as genetic material, DNA hybridization is a key to control the function of DNA-based materials in nanoscience. Since the hybridization of two single stranded DNAs is a thermodynamically favorable process, dissociation of the once formed DNA duplex is normally unattainable under isothermal conditions. As the progress of DNA-based nanoscience, methodology to control the DNA hybridization process has become increasingly important. Besides many reports using the chemically modified DNA for the regulation of hybridization, we focused our attention on the use of a small ligand as the molecular glue for the DNA. In 2001, we reported the first designed molecule that strongly and specifically bound to the mismatched base pairs in double stranded DNA. Further studies on the mismatch binding molecules provided us a key discovery of a novel mode of the binding of a mismatch binding ligand that induced the base flipping. With these findings we proposed the concept of molecular glue for DNA for the unidirectional control of DNA hybridization and, eventually photoswitchable molecular glue for DNA, which enabled the bidirectional control of hybridization under photoirradiation. In this tutorial review, we describe in detail how we integrated the mismatch binding ligand into photoswitchable molecular glue for DNA, and the application and perspective in DNA-based nanoscience.
DNA 的杂交是分子识别中最引人入胜的事件之一，对于生物世代遗传至关重要。除了 DNA 作为遗传物质的功能外，DNA 杂交还是控制基于 DNA 的材料在纳米科学中功能的关键。由于两条单链 DNA 的杂交是一个热力学有利的过程，因此在等温条件下，一旦形成的 DNA 双链体的解离通常是不可实现的。随着基于 DNA 的纳米科学的发展，控制 DNA 杂交过程的方法变得越来越重要。除了许多使用化学修饰的 DNA 来调节杂交的报道外，我们还专注于使用小分子配体作为 DNA 的分子胶。2001 年，我们报道了第一个能够强烈且特异性地与双链 DNA 中的错配碱基对结合的设计分子。进一步研究错配结合分子为我们提供了一个关键发现，即错配结合配体结合的一种新方式，诱导碱基翻转。基于这些发现，我们提出了 DNA 分子胶的概念，用于 DNA 杂交的单向控制，最终得到了光可切换的 DNA 分子胶，使在光照射下可以双向控制杂交。在本教程综述中，我们详细描述了如何将错配结合配体整合到光可切换的 DNA 分子胶中，以及在基于 DNA 的纳米科学中的应用和前景。
