State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210023, P. R. China.
Anal Chem. 2018 Jan 16;90(2):1202-1208. doi: 10.1021/acs.analchem.7b03821. Epub 2017 Dec 21.
Luminescent semiconducting polymer dots (Pdots) have attracted intense attention in the field of electrochemiluminescence (ECL) due to their nontoxic features. For utilizing the nontoxic Pdots to achieve sensitive ECL bioimaging detection, this work studied the ECL behaviors of poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanovinylene-1,4-phenylene)] (CN-PPV) Pdots in aqueous solution, which introduced an electron-withdrawing cyano group to p-phenylenevinylene for enhancing the luminescent efficiency. The CN-PPV Pdots could be both electrochemically oxidized to a positively charged state and electrochemically reduced to a negatively charged state, which led to annihilation of ECL emission. The order of oxidation and reduction greatly influenced the annihilation behavior. In the presence of tri-n-propylamine (TPrA) or SO as a coreactant, the CN-PPV Pdots showed strong band gap ECL emission at 602 nm, which followed two different routes and gave ECL efficiencies of 11.22% and 1.84% (vs Ru(bpy)/TPrA), respectively. The high ECL efficiency allowed CN-PPV Pdots/TPrA system for ECL imaging analysis. As a proof-of-methodology, an ECL imaging method was designed via the chelating interaction of metal ions and Pdots to achieve high selectivity. The proposed ECL imaging chip-based sensor exhibited excellent analytical performance for Fe with a wide linear range from 100 pM to 100 μM and a detection limit of 67 pM. Compared with the ECL methods based on the direct intensity measurement, the developed ECL imaging method possesses the advantages of simplicity, rapid, and high-throughput and has application potential in monitoring water and food quality.
具有发光性能的半导体聚合物点（Pdots）由于其无毒的特性，在电致化学发光（ECL）领域引起了人们的浓厚兴趣。为了利用无毒的 Pdots 实现灵敏的 ECL 生物成像检测，本工作研究了聚[2-甲氧基-5-(2-乙基己氧基)-1,4-(1-氰基乙烯基-1,4-亚苯基)]（CN-PPV）Pdots 在水溶液中的 ECL 行为，该聚合物在对苯撑乙烯基中引入了一个吸电子氰基，以提高发光效率。CN-PPV Pdots 既可以被电化学氧化成带正电荷的状态，也可以被电化学还原成带负电荷的状态，这导致 ECL 发射被消除。氧化和还原的顺序对消除行为有很大的影响。在三正丙胺（TPrA）或 SO 作为共反应物的存在下，CN-PPV Pdots 在 602nm 处表现出强的带隙 ECL 发射，这遵循两种不同的途径，分别给出了 11.22%和 1.84%的 ECL 效率（相对于 Ru(bpy)/TPrA）。高的 ECL 效率使得 CN-PPV Pdots/TPrA 体系可以用于 ECL 成像分析。作为一种方法验证，通过金属离子与 Pdots 的螯合相互作用设计了一种 ECL 成像方法，以实现高选择性。所提出的基于 ECL 成像芯片的传感器对 Fe 具有优异的分析性能，线性范围从 100pM 到 100μM，检测限为 67pM。与基于直接强度测量的 ECL 方法相比，所开发的 ECL 成像方法具有简单、快速和高通量的优点，在监测水质和食品质量方面具有应用潜力。
