Late Transition Metal Photochemistry

该奖项在无机，生物无机和有机化学 该计划支持大卫R博士的无机光化学研究。 麦克米伦，普渡大学化学系。 一个主要目标是 使用发光探针来深入了解 过渡金属配合物嵌入DNA。 各种 取代基将被添加到Cu（II）卟啉，以定制 这些发光材料的激发态寿命和氧化能力， 电荷转移化合物 铜化合物与 发夹形成寡核苷酸将提供关于碱基和 DNA结合相互作用的序列依赖性。 三联吡啶铂 对电子变化非常敏感的信息将被用来识别 影响激发态衰减过程的因素，并区分两个 加合物形成的类型--插层和共价键合--与 B型DNA 插层的电荷转移激发态 复合物被鸟嘌呤淬灭，因此实验还将提供 可能的核酸酶活性的迹象。 过渡金属配合物可以插入到螺旋DNA链中 破坏它的结构和反应性，并且可以破坏链本身。 控制这些复合物的结合， 发生在DNA链上的特定位点， 影响 在这项研究中，将开发发光探针， 鉴定与DNA结合的金属络合物的类型和位置，或者 DNA样蛋白。 这项研究也有一定的相关性， 开发温敏发光涂料。

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.