痕量苯丙胺类毒品蒸气检测用荧光聚合物/金属配合物复合传感材料与纳米器件

Recently,drug detection especially amphetamine derivative detection gained more and more attention. Present detection method including gas chromatography-mass spectrometry could not match the fast and in situ detection requirments. Fluorescent polymer is highly sensitive and fast for detection, but the highly selective polymer with high sensitivity, solubility and air permeability is difficult to design and synthesize. Taken fluoresencent polymer as transducer, metal complex as sensing unit, a composite of fluorescent polymer and metal complex will result in the fluorescent quenching via energy transfer, a followed contact with amphetamine will interrupt the energy transfer and hence recover the fluorescence of fluorescent polymer, then a highly sensitive and selective sensor could be realized easily. The research will includ the following aspects: The selection and optimization of the fluorescent polymer and metal complex composite; The construction of the highly sensitive device and mechanism of evanescent wave excitation of the composites; And the sening mechanism and mechanical process control, et al. The strategies will cover： to select highly efficient and wide band-gap fluorescent polymer as transducer, and metal complex with suitable narrow bandgap and selective nature as sensing unit to construct the composite; to design subwavelength nano optical fibre as waveguid substrate to build the sensing device; and to combine optical waveguide resonant cavity to afford very narrow and amplified emission.By all these research, the drug vapor sensor with high sensitivity and selectivity could be realized, which could also match the fast and in situ detection requirement. The study could provide therotical and data support for sensing material and device design, and give technical support for pubilc safety.

毒品检测尤其是苯丙胺类毒品检测是当前研究的热点，其检测技术包括色质联用等不能满足现场快速检测需要。荧光聚合物传感技术具有高灵敏度和快速响应特点，但特异性材料设计和合成困难。以荧光聚合物为换能器，金属配合物为识别介质，二者先通过能量转移荧光淬灭，毒品蒸气存在并与配合物作用则阻断能量转移并导致体系荧光恢复，从而实现高灵敏和选择性识别。研究包括：荧光聚合物与配合物的选择与结构优化；高灵敏度传感器件的构建及倏逝波激发复合传感材料的物理机制，传感机制研究与过程控制等。选用高效和宽带隙聚合物为换能器，以合适窄能隙和特异的配合物为传感介质构建复合传感材料；以亚波长纳米光纤阵列为波导基底构建高灵敏传感器件，并结合光波导腔产生受激辐射使光谱窄化和信号放大，实现对毒品气体的高灵敏度高选择性识别。研究可为毒品传感材料和高灵敏探测器件的设计提供理论依据和数据支持，为反恐缉毒提供技术支撑。

有机胺是有害污染物，化工原料，毒品成分等，液态爆炸物包括硝酸酯和过氧化物爆炸物易制备，结构不含芳环或硝基难以采用荧光方法检测；神经毒剂是化学战剂和恐怖毒剂。针对三类高危高爆和高毒化学试剂，开展了快速、特异和高灵敏荧光探针的设计合成及传感性能研究。在胺类检测方面，a. 将醛基和三氟乙酰基等多个反应官能团通过共轭方式连接在荧光单元上，首次实现利用单一共轭聚合物分子荧光探针同时实现对多类有机胺蒸气的可逆检测。对不同的胺通过不同峰位像指纹峰一样实现对三类胺蒸气的可逆和高灵敏的识别。探针对胺蒸汽的检测限可达到ppt量级，响应时间几秒，多次重复检测探针性能无衰减。b. 发现了一种新型高效的无需催化和室温条件下的二氰基乙烯基三苯胺/二酯基乙烯基三苯胺与伯胺蒸气间的固/气反应；c. 设计合成了一种8-苄醇芴二倍体荧光传感材料，首次利用固态薄膜探针实现了对冰毒和K粉的直接肉眼可见检测，不同浓度的毒品可根据颜色不同进行识别，肉眼可识别50 pg.cm-2的K粉，可以满足现场直接测试。在液态爆炸物检测方面，a.以八芘代芴二倍体为传感材料，实现了对硝酸酯类爆炸物高灵敏和高选择性探测，以其制备成试纸条，对硝酸酯的检测灵敏度达到0.5 fg/cm2。b.以八面体硅氧烷为核和吸引被分析物分子单元，以八三苯胺芘为发光单元和识别单元与被分析物作用，利用POSS的多反应位点和与爆炸物分子的极性相互作用，实现了对被分析物的选择性和高灵敏快速识别。c. 设计合成了新型多醛基酚胺荧光探针，采用醛基与过氧化物反应产生的羧基加速传感过程，实现了对过氧化物的超高灵敏检测，检测限达0.1ppt。在神经毒剂检测方面，目前文献检测限处于nM或ppm水平。a. 通过设计精巧的ICT型荧光探针分子，实现了对神经毒剂模拟物的肉眼可见的识别，灵敏度达2.6 ppb。b..通过聚集态活化控制传感分子的反应活性，灵敏度进一步达到1.2 ppb。c.通过采用多锚点端基的超支化聚合物分子，探针可以直接测到66 ppt的神经毒剂。可以用于神经毒剂的实时、在线和超高灵敏检测。