核壳型SiQDs@碳点复合材料的制备及其对内源性H2S的多色荧光传感

The imbalance of endogenous hydrogen sulfide in vivo is closely related with the occurrence of many serious diseases. Therefore, the design of accurate, rapid and sensitive H2S recognition sensor is of great significance for studying its physiological and pathological mechanisms. In view of the poor stability, high toxicity and low sensitivity of traditional fluorescent probe for H2S, we are devoted to synthesize core/shell-shaped silicon quantum dots@carbon dots composite materials with low toxicity to achieve multicolor fluorescent detection of endogenous H2S. The core/shell-shaped SiQDs with red fluorescence will be used as internal standard, while the functionalized carbon dots with blue fluorescence will be covalently grafted on the surface of SiO2, and used as response groups to detect H2S. Meanwhile, the interaction mechanism between carbon dots and the functional groups, as well as that between H2S and the composite materials will be discussed. The effect of different ligand on the luminescence performance of carbon dots, as well as that on the recognition performance for H2S will be studied. The sensor with the best recognition performance will be screened out. The successful implementation of this project will provide important data support and theoretical basis for the design and assembly of novel endogenous H2S fluorescence sensors with low toxicity and high efficiency.

内源性硫化氢(H2S)在体内的浓度异常与诸多重大疾病的发生有密切关系。因此，设计准确、快速、灵敏的H2S识别传感器对研究其生理及病理学机制具有重要意义。针对目前H2S荧光传感器发光稳定性差、潜在毒性大、灵敏度低等缺陷，本课题拟合成系列无(低)毒的核壳型SiQDs@碳点复合材料以实现对H2S的快速可视化多色荧光传感。巧妙运用碳点和SiQDs优异的发光特性及无毒性，提出以红色荧光的核壳型SiQDs作为内标，在其壳层引入不同基团修饰的蓝色荧光碳点作为识别H2S的响应基团，通过多色荧光的变化快速识别并定量检测H2S；同时进一步探讨碳点与其表面的功能化基团之间、H2S与复合材料之间的相互作用机理；研究配体结构的差异对碳点发光性能及对H2S识别性能的影响，筛选出识别性能最为优良的荧光传感器。本课题的成功实施将为新型无毒、高效H2S荧光传感器的设计及组装提供重要的数据支持和理论依据。

设计准确、快速、灵敏的识别传感器用于含硫化合物，重金属离子，四环素和DPA等有毒/害物质的即时可视化检测对人类健康具有重要意义。鉴于现有荧光探针普遍存在毒性大，发光稳定性较差，成本高，合成或操作复杂等缺点，开发无毒，低成本和高效的新型荧光探针成为研究热点和难点。.该项目主要研究内容、重要结果及数据如下：.1.基于硅量子点的多色荧光传感器的构建及其对四环素（TC）残留的快速可视化多色荧光传感。所得双响应比例荧光纳米探针SiQDs-Cits-Eu可实现食品中TC残留的可视化多色荧光传感，检测限低至7.1nM。利用彩色扫描APP构建了基于纳米探针固定化试纸的智能手机辅助测试平台。.2.煤基荧光碳点的制备及其荧光传感应用。考察了不同煤源对碳量子点性能的影响，通过表面功能化修饰，制备了系列基于煤基碳点的荧光传感材料，用于TC残留及DPA的多色荧光传感，结合智能手机APP平台，实现了对底物的快速、可视化检测。.3.配体功能化碳点的制备及其对Cu2+和S2-的检测和细胞成像应用。基于邻菲啰啉衍生物功能化碳点实现了对Cu2+和S2−的荧光传感，检测限分别为40.1和88.9nM。此外, 该纳米探针可用于细胞内Cu2+和S2−的成像，显示出在生物学领域的应用前景。 .4.碳点/磷化铟量子点@MOF材料的制备及其对Hg2+和Cys的多色可视化检测。采用一步原位法，构建了蓝光碳点、红光InP/ZnS量子点和MOFs集成的多色纳米传感器CDs/InPQDs@ZIF-8用于连续可视化检测Hg2+和Cys，检出限分别为8.68和37.96nM，满足饮用水和环境水中Hg2+安全监测和控制的要求。此外，结合智能手机APP平台实现了Hg2+和Cys的实时、快速检测。设计了一种逻辑门电路，为纳米传感器在智能器件领域的应用提供了可能性。