Laser-Excited Lanthanide Ion Luminescence in Chemistry and Biophysics ,

该项目将得到生物物理学 程序与无机、生物无机和有机物 化学课程。该项目的重点是开发 在化学和生物物理学中， 溶液中的金属环境，可以从 由于激光激发而发生的发光， 镧系金属离子铽（III）和铕（III）。 重要的生物学信息，例如 血蛋白中的钙离子结合位点， 从这些镧系元素离子的发光的研究， 它们取代了天然金属离子。 激光激发镧系离子发光技术将是 进一步发展，以确定在何种程度上衡量 发光参数（强度，频率， 寿命、分裂）可用于获取有关 存在的不同物种的数量， Eu（III）周围的配体，离子的位置对称性， 配位水分子的数量，能量转移率， 和配体交换动力学。之间的能量转移 发光镧系离子和各种自由扩散 将研究溶液中的无机受体离子， 提供对共振能量机制的理解 转移溶剂对与之结合的Ln（III）离子的可及性 大分子将被探测，并使用Eu（III） 发光作为探针的相互作用的DNA在其 将评估具有金属离子的各种构象。的 t-RNA的结构，其金属离子结合特性，以及 与靶分子的相互作用也将使用 这些方法。模型膜系统的研究 （磷脂双层囊泡）将建立基本的 金属离子与这些系统的相互作用，并允许 离子载体介导的金属离子转运的研究。基本 Eu（III）-羟基物种的配位化学和几种 具有潜在应用的新型螯合剂， 离子载体、NMR成像剂和免疫测定标记将 探讨了一类新的大环配体冠醚亚砜， 将合成和络合与Ln（III）离子探索。

This project will be supported jointly by the Biophysics Program and the Inorganic, Bioinorganic and Organometallic Chemistry Program. The focus of the project is the exploitation in chemistry and biophysics of the information about individual metal environments in solution which can be obtained from the luminescence which occurs as a result of laser excitation of the lanthanide metal ions terbium(III) and europium(III). Imporant biological information, such as the distances between calcium ion binding sites in blood proteins, can be obtained from studies of the luminescence of these lanthanide ions when they are substituted for the native metal ions. Laser-excited lanthanide ion luminescence techniques will be developed further to determine the extent to which measured parameters of the luminescence (intensities, frequencies, lifetimes, splittings) can be used to obtain information about the number of distinct species present, the total charge on the ligands surrounding Eu(III), the site symmetry of the ion, the number of coordinated water molecules, energy transfer rates, and ligand exchange kinetics. Energy transfer between luminescent lanthanide ions and various freely-diffusing inorganic acceptor ions in solution will be investigated to provide an understanding of the mechanism of resonant energy transfer. The accessability of solvent to Ln(III) ions bound to macromolecules will be probed, and the use of Eu(III) luminescence as a probe of the interaction of DNA in its various conformations with metal ions will be assessed. The structure of t-RNA, its metal ion binding characteristics, and interactions with target molecules will be explored also using these methods. An investigation of model membrane systems (phospholipid bilayer vesicles) will establish the basic interactions of metal ions with these systems and allow the study ofionophore-mediated transport of metal ions. The basic coordination chemistry of Eu(III)-hydroxo species and several novel chelating agents with potential applications as ionophores, nmr imaging agents and immunoassay labels will be explored. A new class of macrocyclic ligand, crown sulfoxides, will be synthesized and complexation with Ln(III) ions explored.