Fluorescent Heteroditopic Ligands - Coordination Chemistry, Photophysics, and Sensing Applications

在美国国家科学基金会化学结构、动力学和机理计划(CSDM)的支持下，佛罗里达州立大学的朱磊教授将领导一个研究项目，研究荧光异位配体的基础光物理和配位化学。这项工作可能导致开发荧光指示剂，用于使用荧光显微镜手段的定量分析应用。来自PI实验室的初步数据介绍了基于香豆素的双发射分子作为研究双发射机制的合适的结构平台。在拟议的工作中，将使用稳态和时间分辨光谱实验来揭示解释双重荧光的动力学模型。此外，在异位配基框架中，通过电子受体部分和目标分子之间的工程相互作用可以调节的双重荧光为比率传感器的开发提供了机会。对含有螺内酰胺形式的罗丹明的荧光异位配体的研究将揭示控制含有螺内酰胺的荧光团分子内电子转移效率的因素，以及螺内酰胺开环的动力学。解决这两个问题将促进对罗丹明螺内酰胺化学的基本理解，这为将罗丹明螺内酰胺纳入传感器结构提供了良好的基础。这项授予佛罗里达州立大学朱教授的奖项将导致丰富基础分子光物理和配位化学的知识基础。此外，当荧光团和目标分子之间的特定相互作用被设计到荧光团结构中时，可调双荧光异位配体可以发展成比率荧光传感器。对罗丹明螺内酰胺化学和依赖金属配位的开环动力学的研究将有助于在该体系的基础上进一步开发具有最大信噪比的传感器。拟议活动的一些更广泛的影响来自于国际和平协会致力于教学，并倡导向更广泛的公众传播尖端科学研究。在该奖项的支持下，将开发一门关于化学研究的社会/文化兴趣的课程，面向化学专业的学生和研究生。电影和化学相关博客中与化学和研究生教育相关的内容将作为教材，向广大公众培训年轻的科学传播者。

With the support of an award from the Chemical Structure, Dynamics and Mechanism Program (CSDM) at the National Science Foundation, Professor Lei Zhu at the Florida State University will lead a research program that investigates the fundamental photophysics and coordination chemistry of fluorescent heteroditopic ligands. This work may lead to the development of fluorescent indicators for quantitative analytical applications using fluorescence microscopic means. The preliminary data from the PI's laboratory introduced the coumarin-based dual-emitting molecules as suitable structural platforms for studying the mechanism of dual emission. In the proposed work, steady state and time-resolved spectroscopic experiments will be used to reveal a kinetic model to account for dual fluorescence. Furthermore, dual fluorescence that is tunable via engineered interactions between electron acceptor moieties and a target molecule in a heteroditopic ligand framework offers opportunities for ratiometric sensor development. The proposed investigations on the fluorescent heteroditopic ligands containing a spirolactam form of rhodamine shall reveal the factors that govern the efficiency of intramolecular electron transfer of spirolactam-containing fluorophores, and the kinetics of spirolactam ring-opening. Resolving these two issues will advance the fundamental understanding on the rhodamine spirolactam chemistry, which provides a sound basis for incorporating rhodamine spirolactam in a sensor structure. This award to Professor Zhu at the Florida State University will lead to results that enrich the knowledge base on the fundamental molecular photophysics and coordination chemistry. Furthermore, tunable dual-fluorescing heteroditopic ligands can be developed into ratiometric fluorescent sensors when a specific interaction between the fluorophore and a target molecule is designed into the fluorophore structure. Investigations on the rhodamine spirolactam chemistry and the metal-coordination dependent ring-opening kinetics will aid further sensor development based on this system with a largest possible signal-to-noise ratio. Some of the broader impacts of the proposed activities derive from the PI's commitment to teaching, and to advocating the dissemination of cutting-edge scientific research to the broader public. With the support of this award, a course on the societal/cultural interests on chemical research to chemistry majors and graduate students will be developed. The chemistry- and graduate education-related contents from motion pictures and chemistry-related blogs will be used as teaching materials for training young science communicators to the public at large.