DEVELOPMENT OF HYBRID-TYPE LANTHANIDE COMPLEXES AS EFFECTIVE RECEPTORS

开发了一系列稀土三(β-二酮)和卟啉类化合物作为手性生物底物的有效受体。这些稀土络合物被配位配体电中和，但与各种底物形成高度配位的1：1络合物。我们成功地优化了配位配体和稀土中心的组合，实现了对非发色手性生物底物的特异性识别和传感。基于稀土配位化学，发展了两类特定的受体：(1)稀土三(氟代β-二酮酸盐)提供高效的手性氨基醇的荧光和CD传感；(2)稀土卟啉的额外官能化为多功能生物发生胺和二肽提供了高灵敏的CD探针。由于稀土配合物的设计存在很大的结构差异，本研究揭示的稀土配位化学的新方面为开发一系列涉及智能稀土配合物的新的识别和传感系统提供了潜在的可能性。

A series of lanthanide tris (β-diketonates) and porphyrinates were developed as effective receptors of chiral biological substrates. These lanthanide complexes are electrically neutralized by coordinating ligands but formed highly coordinated 1 : 1 complexes with various substrates. We successfully optimized the combinations of coordinating ligands and lanthanide centers to realize specific recognition and sensing of non-chromophoric chiral biological substrates. Two types of specific receptors were developed based on lanthanide coordination chemistry : (1) Lanthanide tris (fluorinated β-diketonates) provided highly efficient fluorescence and CD sensing of chiral amino alcohols ; (2) Additional functionalization of lanthanide porphyrinates gave highly sensitive CD probes for multi-functional biogenetic amine and dipeptides. Since there are wide structural variations in the design of lanthanide complexes, new aspects of lanthanide coordination chemistry revealed in this study can offer promising possibilities in developing a new series of recognition and sensing systems involving intelligent lanthanide complexes.