基于解聚效应的有机晶体荧光传感材料及其冰毒检测应用

Drug detection, especially methamphetamine and other synthetic drugs, is the difficulty of current detection technology. Fluorescence sensing, with its advantages of high sensitivity, high selectivity and fast response, has a wide application prospect in the fields of anti-terrorism and drug control. However, the traditional fluorescent probes are mainly based on host-guest interaction, and trace guest molecules can only cause weak changes of the host structure, which makes the design of ultra-sensitive sensing materials very challenging..The crystal and molecular state properties of organic fluorescent substances are greatly different, therefore, organic fluorescent molecules can be regulated into metastable crystal structure through orderly assembly. When interacting with the target guest molecules, the metastable crystal can be induced to release interface energy and selectively disaggregate, leading to significant fluorescence changes and ultra-sensitive object recognition..This project intends to take methamphetamine as the detection object, and the main research contents include: design and synthesis of block sensing molecular structure; Control of different template molecules and crystallization microenvironment for ordered assembly of the sensitive structures of metastable crystals, based on; Clarify the deep mechanism and regulation means of interface host-guest interaction, utilizing fluorescent spectroscopy and ultrafast spectroscopy to online detect the change of crystal luminescence performance, and ssisted by quantum chemistry and dynamics simulation. On this basis, realize the ultra-sensitive detection of methamphetamine for appliction. This study can provide a brand new way to explore new fluorescence sensitive materials.

毒品检测尤其是冰毒等合成型毒品，是当前检测技术的难点。荧光传感以其灵敏度高、选择性强、响应速度快等优势，在反恐、禁毒等领域有着广泛的应用前景。但传统的荧光探针主要基于主客体相互作用，痕量客体分子仅能引起主体的微弱变化，使得超高灵敏度敏感材料的设计具有很大的挑战性。.有机荧光物质，其晶态与分子态性能差异巨大，可以通过有序组装形成亚稳态晶体结构，当与目标客体分子作用时，诱发界面能释放与晶体高选择性解聚，导致显著荧光变化，实现超灵敏客体识别。.本项目拟以冰毒为检测对象，主要研究内容包括：砌块传感分子结构设计与合成；利用不同模板分子或成晶微环境调控，实现晶体敏感结构的有序组装；利用超快光谱等在线检测其晶态发光性能变化，通过量子化学及动力学模拟辅助，阐明界面主客体作用的深层机制及调控手段，实现对冰毒分子的超灵敏检测。本研究可为探索新的荧光敏感材料提供全新的路径。

毒品检测尤其是冰毒等合成型毒品，是当前检测技术的难点。荧光传感以其灵敏度高、选择性强、响应速度快等优势，在反恐、禁毒等领域有着广泛的应用前景。但传统的荧光探针主要基于主客体相互作用，痕量客体分子仅能引起主体的微弱变化，使得超高灵敏度敏感材料的设计具有很大的挑战性。本项目主要基于有机晶体界面的特殊理化性质，围绕晶体界面解聚效应，进行了超高灵敏度传感策略与体系的设计与研发，执行期间发表SCI论文9篇，申请专利3项，很好的完成了既定任务。主要有以下几大方面研究成果：.1.物理型手性晶体界面解聚体系：.通过R型和S型手性芘乙醇分子作为荧光砌块，自组装构筑具有手性氢键链的功能晶体界面，获得具备手性识别能力的物理型晶体界面解聚荧光传感体系，实现了冰毒两种手性异构体的高特异性检测，检测限达154 fg/ml，专利已授权，原型检测设备已经进入定型调试阶段，有望取得较好的应用前景；同时，发现了类多巴胺转运蛋白的特征传感模式，并通过仿生晶体界面设计，实现了对多巴胺的灵敏检测，检测限低至1.06 ng/ml。.2.化学反应型晶体界面解聚探针：.通过有机晶体界面调控，将无反应活性惰性芳香硼酸分子，组装为高化学活性的有序界面，实现了化学反应型晶体界面解聚效应，实现有机胺的可视化实时监测，检测限低至3.3μM，工作发表在Chemical Communications上。.3.界面发光与界面解聚气相传感新策略：.从晶体界面解聚效应出发，我们进一步深入理解源于界面结构的全新理化性质，基于二维氢键晶格网络结构实现超长寿命发光，寿命达到0.45s，量子效率达26%，并支持低成本柔性印刷，工作发表在ACS Applied Materials & Interface上。最后，结合界面发光策略和晶体界面解聚效应，构建了冰毒气相传感的原位磷光体系，通过在界面原位诱导聚集态发光结构变化，将液相的界面解聚效应推广到超高灵敏度气相检测方向，成功实现了首例发光寿命模式毒品传感器件，寿命模式检测限达0.11 ppt，比强度模式13.4 ppb低5个数量级，在毒品快速检测应用方向上具有重要意义，工作发表在Analytical Chemistry上。