半导性聚合物量子点的电致化学发光及其生物传感研究

The development of electrochemiluminescence (ECL) is closely focused on the exploitation and application of new ECL luminophores. Aiming at the problems of poor biocompatibility, low quantum efficiency and difficult regulation of conventional inorganic semiconducting nanoemitters as ECL nanoemitters, this project plans to develop non-toxic semiconducting polymer dots (Pdots) as novel nanoemitters and explore its new application in biosensing. Through introducing electron-withdrawing groups to reduce the bandgap of semiconducting polymers, the Pdots with near infrared ECL spectral properties is developed. Through introducing aggregate-induced emission (AIE)-active groups into the semiconducting polymer backbone, ECL with AIE enhancing properties are obtained. Owing to further control excitation potential and emission intensity of this Pdos, the donor-acceptor electronic structure was designed into semiconducting polymer. By studying the relationship between the composition, structure and ECL properties of these novel Pdots, the purpose of this study is to lay the foundation for the development of near-infrared, highly efficient, tunable Pdots-based nanoemitter. Utilizing excellent Pdots with the integration of specific biological recognition interaction and signal amplification methods, this project paves for developing the highly specific and sensitive biosensing application for tumor biomarkers.

电致化学发光（electrochemiluminescence, ECL）领域的发展紧紧围绕着新型ECL发光体的开发与应用。针对传统无机半导性纳米发光体的生物相容性差、ECL量子效率不高和性质难以调控等问题，本项目拟开发基于无毒的半导性聚合物量子点（polymer dots, Pdots）作为新型纳米发光体并探索其在生物传感上的应用。通过引入吸电子基团降低半导性聚合物的带隙，发展近红外ECL光谱性质的Pdots；通过将聚集诱导发射活性基团引入聚合物骨架，获得具有AIE增强性质的ECL。利用给体-受体电子结构设计来进一步调控该Pdos的激发电位和发射强度。通过深入研究这些新型Pdots的组成、结构与ECL性质之间的关系，目的是为开发近红外光谱的、高效的、性质可调的Pdots基纳米发光体奠定基础。结合特异性生物识别作用和信号放大方法，最终实现肿瘤标志物的高特异性、高灵敏的生物传感应用。

近年来，无毒性和环境友好的半导性聚合物量子点（Pdots）作为一种新型的电化学发光（ECL）纳米发光体受到重点关注。但目前所发展的Pdots基纳米发光体还存在激发电位高、ECL发射强度弱和生物传感应用少等普遍问题。因此开发和利用性能更加优异的Pdots纳米发光体尤为重要。本项目通过分子设计和化学合成，发展更低激发电位和更高发射强度的新型Pdots基纳米发光体，结合信号放大新策略，应用于生物分子的检测。. 在开发新型Pdots纳米发光体方面，合成了新型聚集诱导发射（AIE）活性的共轭聚合物，通过给体（Donor）-受体（acceptor）电子结构实现了Pdots激发电位和发光强度的调控；合成了鲁米诺类似物共价功能化Pdots，基于共振能量转移策略实现了Pdots激发电位的有效降低。在生物传感应用方面，探索了金磁纳米粒子和聚合物量子点二聚体调控的ECL体系，基于电位分辨ECL以期实现两种microRNA的同时检测；探索酶促聚多巴胺沉积技术实现microRNA的高灵敏检测；利用所合成的鲁米诺类似物功能化的Pdots并结合ECL成像技术，实现了血糖的快速检测。. 本项目的研究将为开发性能更加优异的Pdots基纳米发光体以及构建高灵敏的生物分析体系方面提供有益借鉴。