新型超分子发光受体的合成及其分子识别功能研究

Development of high sensitive, high selective fluorescence probes is an intrinsic subject in study of luminescent sensors, DNA chips and nanoparticle-based biosensors. Under the financial support of the National Natural Science Foundation of China, we developed molecular recognition methods for biologically important amino acid derivatives, DNA, sugars, as well as for alkali metal ions and dicarboxylate anions by synthesized artificial receptors or commercially available reagents. Using zinc(II) protoporphyrin (ZnPP) as a luminescent functional monomer, a histamine-selective molecularly imprinted fluorescent polymer was synthesized. We also noticed that ZnPP can provide multi-binding sites, the central atom zinc provides a coordinate binding site and the peripheral carboxylic acid groups provide charge interaction and hydrogen binding sites. Selective recognition of histamine and ctDNA in water with ZnPP was thus achieved. We also found that ZnPP is a promising phosphorescent probe for DNA in water. A solid-substrate room temperature phosphorescence method for DNA determination was established in the absence of a heavy atom perturber. Hydrogen bonding and coordination interaction play a crucial role in the host-guest interaction. This work was introduced by the annual review of Analytical Chemistry in 2002. A novel boronic acid fluorophore/b-cyclodextrin complex sensor has also been developed for sugar recognition in water at neutral pH. Fluorescence intensity increased in the presence of sugars with this complex sensor via a PET type response mechanism. These studies are helpful for the further investigations such as detection of SNPs, ssDNA and dsDNA, as well as related genetic nucleic acids for drug delivery.

本研究旨在通过分子设计开发能在水相或液/ 液界面进行高选择性分子识别的新型超分子发光人工受体。由具有不同官能团的主体分子经自组装形成的分子组合体通过氢键作用在液/液界面对客体分子实现选择性的多点识别；通过分子印记法合成具有分子记忆功能的发光性环糊精串联分子集合体，实现对某些大尺寸生理活性及环境毒性物质的高选择性识别。