酰腙希夫碱稀土Er3+/Yb3+上转换发光配合物的制备及癌细胞成像的微量热学研究

开发光学性能优越的荧光分子探针用于癌细胞的定向识别与成像、并对其成像机制进行研究意义重大。本课题选择配位能力强、配位模式丰富的酰腙类希夫碱配体作为敏化发光中心的基质材料，通过掺杂具有近红外发光特性的稀土Er3+/Yb3+离子，设计组装新型稀土配合物类上转换发光材料，引入不同官能团修饰配体获得结构多样的稀土配合物，调节稀土离子的比例对配合物的发光性能进行调控，通过晶体学和光谱学手段获得结构信息和光学指标，筛选性能优异的配合物开展体外活体癌细胞的光成像研究，关联结构和性能讨论构效关系。利用微量热技术对配合物的细胞成像历程实施动态跟踪，探寻细胞成像与热力学的关系，揭示成像机制及其热力学驱动内因，确定成像行为的能量控制因素，获悉配合物与细胞的协同性和指向性，实现配合物癌细胞成像靶向性和选择性的精准控制。系统的细胞成像和热力学研究对设计和合成高性能发光材料及揭示细胞成像本质具有重要的理论及应用意义。

It is significant to develop excellent fluorescent molecular probe for targeted recognition and imaging of cancer cell and investigation of imaging mechanism. In present project, acylhydrazone Schiff bases with superior chelate effect and diverse coordination modes are selected as organic host materials to sensitize luminescent ions, while Er3+ and Yb3+ ions that feature the near-infrared luminescence are identified to be coordination centers in the system. The integration of the above two candidates will be employed to design and assemble novel upconversion luminescent complexes. Fine-tuning of the structures and luminescence of target products would be modulated by modification of the ligands and alteration of the metal ratio. The structural characteristics and luminescent properties will be recorded by spectroscopy and crystallography. The high-performant Er3+/Yb3+ complexes can be adopted to perform the optical imaging of living cancer cells in vitro. As a result, the structure-function relationship will be explored by the association of structure and property. Dynamic tracing in the imaging behaviors of Er3+/Yb3+ luminescent complexes will be carried out by using microcalorimetry measurement system, which is conductive to extracting the thermodynamic data of the processes and exploring the relationships between imaging behaviors and thermodynamic properties. The results of the investigation would reveal the imaging mechanism and thermodynamic internal cause, as well as determine the energetic controlling factor of imaging, which are helpful to illuminate the cooperativity and directivity between complex and cell, and achieve an accurate control for the targeted and selective cancer imaging of the rare earth complexes. Systematic studies on cellular imaging and thermodynamics are expected to provide essentially theoretical and practical significances for designing and synthesizing outstanding luminescent materials and understanding the nature of living cellular imaging.