基于中间体和光发射体间能量传递机制实现碳纳米点基高亮化学发光的研究

At present, carbon nanodots (CDs) based chemiluminescence (CL) has important potential applications in many fields such as ultra sensitive analysis, cold light source and so on, which really matter to national defense and people's livelihood. However, due to the inefficiency in CL of CDs, there is still lack of significant breakthrough that can make CDs based CL performs high detection sensitivity and selectivity. In view of the above problems, we plan to design and construct an oxalic ester-hydrogen peroxide-CDs CL system, employing CDs as the light emitter and marker by virtue of the easy adjustment of their band gap. In this system, we will select the appropriate oxalate as CL intermediates. At the same time, we will achieve a reasonable energy level matching between CL intermediates and CDs by changing the light emission band gap of CDs, which needs regulating the chemical content of different elements and the conjugation of kernel in CDs. We will solve the problem on the effective injection of the electron and hole from high-energy intermediate to the light emitter in order to improve the efficiency of chemical energy into light energy conversion in this system. Meanwhile, the modification on the surface of CDs though functional groups is applied to achieve proper lipophilic and hydrophilic properties and high selectivity. Finally，we will achieve efficient CL and high sensitive analysis detection based on CDs. This project will provide new ideas for the research and development of CDs based CL system.

目前，碳纳米点基化学发光在超灵敏分析检测、冷光源等关乎国防、民生的众多领域具有重要的潜在应用。然而所得碳纳米点基化学发光效率低，严重阻碍了其在化学发光分析检测方面的应用。针对以上问题，本项目提出利用碳纳米点自身带隙易调节的特点，以此作为化学发光过程中光发射体和发光标记物，设计并构建草酸酯-过氧化氢-碳纳米点化学发光体系。在该体系中，优化选取草酸酯化学发光中间体，并通过对不同元素的化学含量和内核的共轭程度调控完成对碳纳米点发光带隙调节来实现与碳纳米点光发射体间的能级匹配，解决高能中间体到光发射体间电子和空穴的有效注入这一难题，以此提升该体系化学能到光能的转换效率；同时通过表面基团改性实现对碳纳米点亲水亲油性质以及对待测物质选择性的改善，有望实现碳纳米点基高效化学发光和高灵敏分析检测应用。该项目的开展为推动碳纳米点化学发光体系的发展提供新的思路。

目前，碳纳米点基化学发光在超灵敏分析检测、冷光源等关乎国防、民生的众多领域具有重要的潜在应用。然而所得碳纳米点基化学发光效率低，严重阻碍了其在化学发光分析检测方面的应用。针对以上问题，本项目提出利用碳纳米点自身带隙易调节的特点，以此作为化学发光过程中光发射体和发光标记物，设计并构建草酸酯-过氧化氢-碳纳米点化学发光体系。在该体系中，优化选取草酸酯化学发光中间体，并通过对不同元素的化学含量和内核的共轭程度调控得到了红绿蓝三色发光碳纳米点，其发光带隙可调谐，并可与化学发光中间体能级匹配，解决高能中间体到光发射体间电子和空穴的有效注入这一难题，实现了该体系化学能到光能的转换效率目前报道的最高值（9.32 × 10(−3) 爱因斯坦每摩尔），亮度可达3.28 坎德拉每平方米。另外，通过将碳纳米点表面基团改性和进一步碳化实现对其亲水亲油性质转换和具有生物组织穿透性能良好的近红外发射，进一步将碳纳米点与草酸酯交联成聚合纳米粒子得到了具有高效化学发光纳米传感器；该传感器可对活性氧（过氧化氢）在动物体内和体外实现高灵敏和高选择性检测，并在小鼠体内实现可达5纳摩的纪录性检测限；更进一步利用炎症模型小鼠实现该化学发光探针对腹腔炎症的监测。该项目的开展为推动碳纳米点化学发光体系的先进信息加密和记录，疾病诊疗方面提供了新思路。相关工作整理发表了SCI文章12篇，其中包括在本专业权威期刊Advanced Science（2篇）,　Advanced Optical Materials（1篇）和Carbon（3篇）等上发表相关研究成果。申请国家发明专利2个。