Molecular Wires Based on Metal-Modified Oligonucleotides

该项目的主要目标是合成、表征和优化结合结构多样性和电响应的分子，以便在纳米电路的构建中实现。由于碳纳米管和DNA本身都不能自发地产生一个明确的策略，使它们杂交成能够自组装的集成分子线，我们的研究重点是两个有前途的替代方案：我们将开发的第一类化合物被描述为金属修饰的寡核苷酸（MMOs），第二类是自组装的金属有机框架（mof）。MMOs是通过将化学合成的具有更高金属离子亲和力的核苷衍生物引入DNA寡核苷酸并随后加入金属离子来制备的。金属离子的实现是至关重要的，因为它们将使电荷沿着DNA传输。相反，mof由一维金属聚合物组成，例如由合适的核碱基衍生物结合在一起。作为桥接有机配体的替代品，也可以使用无机桥，从而产生无机-有机杂化材料（由于其固有的两种金属M和一个配体X的序列而称为MMX聚合物）。当将具有匹配氢键模式的配体结合到MMX聚合物中时，这些配体可以作为自组装过程的起始化合物，使用其他系统（如寡核苷酸）作为支架。一旦分子线的行为被证实，一个简单的装置将被测试。

The main goal of this project is to synthesize, characterize, and optimize molecules that combine structural diversity and electrical response for an implementation in the construction of nanocircuits. Since neither carbon nanotubes nor DNA by itself spontaneously yield a clear strategy for their hybridization into ¿integrated¿ molecular wires capable of self-assembly, our research focuses on two promising alternatives: The first class of compounds that we will develop is described best as metal-modified oligonucleotides (MMOs), and the second class as self-assembling metal-organic frameworks (MOFs). MMOs are prepared by introducing chemically synthesized nucleoside derivatives with increased metal ion affinity into DNA oligonucleotides and subsequently incorporating metal ions. Implementation of metal ions is crucial as they will enable the charge transport along the DNA. MOFs instead consist of a one-dimensional metal polymer held together by e.g. a suitable nucleobase derivative. As an alternative to a bridging organic ligand, also inorganic bridges can be used, thus yielding inorganic-organic hybrid materials (referred to as MMX polymers due to their inherent sequence of two metals M and one ligand X). When incorporating ligands with a matching hydrogen bonding pattern into MMX polymers, these can serve as starting compounds for the self-assembly process using other systems such as oligonucleotides as a scaffold. Once the molecular-wire behavior is proven, a simple device will be tested.