Late Transition Metal Photochemistry

这个无机、生物无机和有机金属化学项目的奖项支持普渡大学化学系David R. McMillin博士在无机光化学方面的研究。一个主要的目标是使用发光探针来深入了解过渡金属配合物插入DNA的要求。将各种取代基添加到Cu（II）卟啉中，以调整这些发光、电荷转移化合物的激发态寿命和氧化能力。铜化合物与形成发夹的寡核苷酸的相互作用将为dna结合相互作用的碱基依赖性和序列依赖性提供信息。对电子变化非常敏感的铂（II）三吡啶将被用来识别影响激发态衰变过程的因素，并与b型DNA区分两种类型的加合物形成——插层和共价键。鸟嘌呤抑制了嵌入复合物的电荷转移激发态，因此实验也将提供可能的核酸酶活性指示。过渡金属配合物可以插入螺旋DNA链，破坏其结构和反应性，并可以破坏链本身。控制这些复合物的结合，从而在DNA链上的特定位点发生破坏或切割，具有重要的药学意义。在这项研究中，将开发发光探针来识别与DNA或DNA样蛋白结合的金属复合物的类型和位置。本研究对温敏发光涂料的开发也有一定的指导意义。

This award in the Inorganic, Bioinorganic, and Organometallic Chemistry Program supports research in inorganic photochemistry by Dr. David R. McMillin, Chemistry Department, Purdue University. A major objective is to use luminescent probes to gain insight into the requirements for intercalation of transition metal complexes into DNA. Various subsituents will be added to Cu(II) porphyrins in order to tailor the excited state lifetimes and oxidizing abilities of these luminescent, charge transfer compounds. The interaction of the copper compounds with hairpin-forming oligonucleotides will provide information on base and sequence dependence of DNA-binding interactions. Pt(II) terpyridines that are very sensitive to electronic changes will be used to identify factors affecting excited-state decay processes and to distinguish two types of adduct formation--intercalation and covalent bonding--with form-B DNA. The charge-transfer excited state of the intercalated complex is quenched by guanine, so the experiments will also provide indications of possible nuclease activity. Transition metal complexes can insert into a helical DNA strand disrupting its structure and reactivity and can break the strand itself. Controlling the binding of these complexs so that disruption or cleavage occurs at particular sites on the DNA chain has important pharmaceutical implications. In this research, luminescent probes will be developed to identify the type and location of metal complex binding to DNA or DNA-like proteins. This research also has some relevance to the development of temperature-sensitive luminescent paints.