School of Chemistry & Institute for Life Sciences, University of Southampton , Highfield, Southampton SO17 1BJ, U.K.
Acc Chem Res. 2017 Apr 18;50(4):823-831. doi: 10.1021/acs.accounts.6b00583. Epub 2017 Mar 8.
DNA is well-known as bearer of the genetic code. Since its structure elucidation nearly seven decades ago by Watson, Crick, Wilkins, and Franklin, much has been learned about its detailed structure, function, and genetic coding. The development of automated solid-phase synthesis, and with it the availability of synthetic DNA with any desired sequence in lengths of up to hundreds of bases in the best case, has contributed much to the advancement of the field of DNA research. In addition, classic organic synthesis has allowed introduction of a very large number of modifications in the DNA in a sequence specific manner, which have initially been targeted at altering the biological function of DNA. However, in recent years DNA has become a very attractive scaffold in supramolecular chemistry, where DNA is taken out of its biological role and serves as both stick and glue molecule to assemble novel functional structures with nanometer precision. The attachment of functionalities to DNA has led to the creation of supramolecular systems with applications in light harvesting, energy and electron transfer, sensing, and catalysis. Functional DNA is clearly having a significant impact in the field of bioinspired nanosystems. Of particular interest is the use of porphyrins in supramolecular chemistry and bionanotechnology, because they are excellent functional groups due to their electronic properties that can be tailored through chemical modifications of the aromatic core or through insertion of almost any metal of the periodic table into the central cavity. The porphyrins can be attached either to the nucleobase, to the phosphate group, or to the ribose moiety. Additionally, noncovalent templating through Watson-Crick base pairing forms an alternative and attractive approach. With this, the combination of two seemingly simple molecules gives rise to a highly complex system with unprecedented possibilities for modulation of function, and with it applications, particularly when combined with other functional groups. Here, an overview is given on the developments of using porphyrin modified DNA for the construction of functional assemblies. Strategies for the synthesis and characterization are presented alongside selected applications where the porphyrin modification has proven to be particularly useful and superior to other modifiers but also has revealed its limitations. We also discuss implications on properties and behavior of the porphyrin-DNA, where similar issues could arise when using other hydrophobic and bulky substituents on DNA. This includes particularly problems regarding synthesis of the building blocks, DNA synthesis, yields, solubility, and intermolecular interactions.
DNA 是众所周知的遗传密码载体。自沃森、克里克、威尔金斯和富兰克林近 70 年前阐明其结构以来，人们已经了解了它的详细结构、功能和遗传编码。自动化固相合成的发展，以及随之而来的具有任意所需序列的合成 DNA 的可用性，长度可达数百个碱基，在 DNA 研究领域的发展中做出了巨大贡献。此外，经典的有机合成允许以序列特异性的方式在 DNA 中引入大量修饰，这些修饰最初旨在改变 DNA 的生物学功能。然而，近年来，DNA 已成为超分子化学中一种极具吸引力的支架，在该化学中，DNA 脱离其生物学作用，充当 stick 和 glue 分子，以纳米精度组装新的功能结构。将官能团附着到 DNA 上导致创建了具有应用于光捕获、能量和电子转移、传感和催化的超分子系统。功能性 DNA 显然在仿生纳米系统领域产生了重大影响。特别有趣的是卟啉在超分子化学和生物纳米技术中的应用，因为它们是极好的功能基团，因为它们的电子性质可以通过对芳核的化学修饰或通过将周期表中的几乎任何金属插入到中心腔中来进行调整。卟啉可以连接到碱基、磷酸基团或核糖部分。此外，通过 Watson-Crick 碱基配对的非共价模板形成了另一种有吸引力的方法。通过这种方式，将两个看似简单的分子结合起来，形成了一个具有前所未有的功能调节可能性的高度复杂系统，并且具有应用，特别是与其他功能基团结合时。在这里，概述了使用卟啉修饰的 DNA 构建功能组装体的发展。介绍了合成和表征策略以及选定的应用，其中卟啉修饰已被证明特别有用且优于其他修饰剂，但也揭示了其局限性。我们还讨论了对卟啉-DNA 性质和行为的影响，当在 DNA 上使用其他疏水性和大体积取代基时，也可能会出现类似的问题。这包括特别是关于构建块合成、DNA 合成、产率、溶解度和分子间相互作用的问题。
