Coordination polymer approach to DNA functionalisation and assembly

生物自组装，即分子将自己组织成定义明确的功能结构和层次系统，激发了材料合成和器件制造的新方法。这些所谓的自下而上的方法提供了降低成本、减小尺寸以及增加功能和复杂性的可能性。这些方法中最成功的是那些基于DNA的方法，DNA是生物学的信息载体。DNA的强大性质，可靠的合成，可控的长度尺度，结合对遗传密码的结构构建规则的深刻理解，解决了材料设计工具包所需的许多标准。然而，天然生物聚合物缺乏一系列有趣的物理化学性质;其电子系统相对静止。为了克服这一点，已经制定了各种战略。最广泛采用的是将预合成的组分如纳米颗粒、化学修饰或金属和无机材料直接沉积到DNA上以形成电线。在本提案中，我们将探索一种新的基于分子的方法，用于制备功能化的基于DNA的材料和自组装分子结构，这也为简单的基于DNA的电子学提供了一条可能的途径。这种方法将使用修饰的DNA成分，硫代糖苷，与天然生物聚合物相比具有不同的金属结合特性。这些硫代配体可以将金属离子组装成延伸的链，形成所谓的配位聚合物，其具有有用的光电性质，包括导电性。利用这种方法，该项目旨在开创一种新型材料，将这些功能配位聚合物与DNA结合起来。这些金属基聚合物可以同时引入发光、折射率和独特的手性光学性质。此外，它们在结构的部分中建立热稳定的连接，将可寻址的导电区域引入分子结构以及潜在的新反应性位点。通过允许通过这种新的路线引入新的特性，新类型的构造协议、组成结构和材料特性的组合将是可能的。因此，该项目将推动自下而上的分子设计领域，特别是基于DNA的材料，朝着增加功能的方向发展，从而为未来的发展扩展可用的工具包。

Biological self-assembly, whereby molecules organise themselves into well-defined functional architectures and hierarchical systems, has inspired new approaches to materials synthesis and device fabrication. These, so-called, bottom-up methods offer the possibility of lower cost, smaller size and increased functionality and complexity. Among the most successful of these methods are those based on DNA, biology's information carrier. DNAs robust nature, reliable synthesis, controllable length scale, combined with the deep understanding of the genetic code's structure-building rules address many of the criteria desired of a materials design toolkit. However, the native biopolymer lacks a range of interesting physico-chemical properties; its electronic system is relatively quiescent. To overcome this various strategies have been developed. Most widely adopted are the incorporation of pre-synthesized components such as nanoparticles, chemical modification, or deposition of metals and inorganic materials directly onto the DNA to form electrical wires, for example. In this proposal we will explore a new molecular-based approach for preparing functionalized DNA-based materials and self-assembled molecular architectures that also offers a possible route to a simple DNA-based electronics. This approach will use modified DNA components, thionucleosides, that have different metal-binding properties compared to those of the native biopolymer. These thionucleosides can assemble metal ions into extended chains forming, so-called, coordination polymers which have useful optoelectronic properties, including electrical conductivity. Using this approach, the project aims to pioneer a new type of material that combines these functional coordination polymers with DNA. These metal-based polymers can introduce, at once, luminescence, semiconductivity and distinct chiral optical properties. Furthermore, they establish thermally-stable linkages into the parts of the structure, introduce addressable electrically-conducting regions into the molecular architecture and also sites of potential new reactivity. By allowing the incorporation of new properties via this novel route new types of construction protocol, compositional architectures and combinations of material properties will be possible. As a result the project will advance the field of bottom-up molecular design, specifically DNA-based materials, towards increased functionality and so expand the available toolkit for future developments.