Development of Nano-Sized Lanthanide Complexes for Supramolecular Recognition

镧系配合物作为特殊的催化剂、有效的MRI试剂和其他基于独特化学和物理性质的功能器件受到了广泛的关注。其中，发光镧系配合物在阴离子传感、基因组和蛋白质组学筛选、生物成像等技术方面有进一步的应用。除了长寿命、高强度和线形发光外，它们还具有多种配位数和多种配位结构，这为进一步的复杂设计提供了一种新的、有效的策略。我们证明了几种镧系配合物在与共存物种高度配位时改变了它们的结构和化学计量，并成功地将它们作为纳米尺度客体物种的选择性和发光受体。设计了一种新型的三脚配体，以提供阴离子依赖的镧系络合和发光。它们的树状衍生物被进一步开发用于阴离子反应的镧系配合物的功能化。这同时纳入了几个镧系离子响应共存阴离子，并表现出客依赖的近红外发光响应。基于镧系复合物的SPR方法对his标记的蛋白进行了高度的传感，镧系复合物受体与靶蛋白的低聚组氨酸片段之间发生了高度协调的络合。这些结果清楚地表明，镧系元素配位化学可以为开发纳米级分子识别系统提供有效的策略。

Lanthanide complexes have received recent attention as specific catalysts, effective MRI reagents, and other functional devices based on unique chemical and physical properties. Among them, luminescent lanthanide complexes offered further applications in anion sensing, genomic and proteomic screening, biological imaging and related technologies. In addition to long-lived, highly intense, and line-shaped luminescence, they have a wide variety of coordination numbers and versatile coordination structures, which can provide a new, effective strategy for further sophistications.We demonstrated that several lanthanide complexes altered their structures and stoichiometries upon highly coordinated complexation with co-existing species, and successfully applied them as selective and luminescent receptors for nano-scaled guest species. A novel type of tripode ligands were designed to provide anion-dependent lanthanide complexation and luminescence. Their dendrimer derivative was further developed for functionalization of anion-responsive lanthanide complexes. This simultaneously incorporated several lanthanide cations in response to co-existing anions, and exhibited guest-dependent near-infrared luminescence responses. His-tagged protein was highly sensed by lanthanide complex-based SPR method, in which highly coordinated complexation between lanthanide complex receptor and oligohistidine moiety of the targeted protein significantly occurred. These results clearly indicate that lanthanide coordination chemistry can offer an effective strategy for development of nano-size molecular recognition systems.