Structurally Diverse Molecular Architectures with Unusual Excited State Dynamics and Reactivity Providing Multifunctional Interactions with DNA

无机络合物，如顺铂，与DNA的相互作用构成了调控这一关键生物分子的反应性和分子生物学的主要入口点。在这个由化学结构、动力学和机理计划资助的项目中，凯伦·布鲁尔教授将使用大量灵敏的方法设计、制备和研究一组结构不同的无机络合物，这些络合物与DNA发生多条反应路径。将制备一系列具有多功能反应活性的新结构基序，以扩大已知分子的结构多样性，并创建一大类超分子，每个亚单位对其调节某些性质或执行某些功能，从而导致具有非常复杂功能的分子机器。了解和控制每个亚单位对这些不寻常的多功能分子的性质和反应性的作用，包括用低能量红光激发的不寻常的系统。该项目将探索这些体系的多方面反应能力，包括与DNA的热结合，通过新的机制可见光诱导DNA光结合，红光激活的DNA光裂解，以及DNA修饰的新范式-DNA光压缩。发现调节DNA活性的新材料在医学上有许多应用，包括遗传和传染病的治疗。此外，这种具有多条反应路径的复杂分子的开发组装而成的知识库在许多领域都有应用，包括生物分子的修饰和检测、分子传感、光和氧化还原激活的分子电子学、光能到化学能的转化和金属基催化。

The interaction of inorganic complexes, e.g., cis-platin, with DNA constitutes a major entry point into modulating the reactivity and molecular biology of this critical biomolecule. In this project funded by the Chemical Structure, Dynamics and Mechanism Program, Prof. Karen Brewer will design, prepare and study a group of structurally diverse inorganic complexes which undergo multiple reaction pathways with DNA, using a large array of sensitive methods. A series of new structural motifs with multifunctional reactivity will be prepared to expand the structural diversity of known molecules and create a large class of supermolecules for which each sub-unit modulates some property or performs some function that leads to molecular machines with very complex functions. Understanding and controlling the role of each sub-unit on the properties and reactivity of these unusual multifunctional molecules will be undertaken, including unusual systems that are excited with low energy red light. The project will explore the multifaceted reactivity of these systems including thermal binding to DNA, visible light-induced DNA photobinding via new mechanisms, red light activated DNA photocleavage, and a new paradigm for DNA modification, DNA photocondensation.The discovery of new materials which modulate the activity of DNA has many applications in medicine, including the treatment of genetic and infectious diseases. In addition, the knowledge base assembled by the development of such complex molecules with multiple reaction pathways is applicable in many fields, including the modification and detection of biomolecules, molecular sensing, light and redox activated molecular electronics, conversion of light energy to chemical energy and metal based catalysis.