Center for Advanced Analytical Science, School of Chemistry and Chemical Engineering, Guangzhou Key Laboratory of Sensing Materials & Devices c/o School of Civil Engineering, Guangzhou University, Guangzhou 510006, China.
Analyst. 2022 May 30;147(11):2442-2451. doi: 10.1039/d2an00352j.
To achieve the most efficient, all-exciton-harvesting organic electrochemiluminescence (ECL) for biosensing, aqueous thermally activated delayed fluorescence (TADF)-ECL (aqueous TADF-ECL) was successfully launched to provide a breakthrough for the theoretical ECL efficiency limitation of aqueous fluorescence ECL (aqueous FL-ECL). However, achieving efficient TADF emitters suitable for aqueous TADF-ECL remains challenging. A previous strategy relied on TADF small molecular nanoparticles (NPs). However, the aggregation caused quenching of such TADF molecules within NPs is intense, which renders such NPs inefficient for ECL emission. Herein, we propose developing conjugated polymer dots (Pdots) based aqueous TADF-ECL. Compared to the intrinsic TADF polymer, the Pdots achieve a comparable TADF photophysical properties in water, , the comparable PL spectra, similar PL quantum efficiency () and intense delayed fluorescent contributions a fast reverse intersystem crossing rate () of 1.5 × 10 s. The resultant relative ECL efficiency () of the oxidative-reduction ECL system (CO as the co-reactant) is as high as 11.73% ( the Ru(bpy) counterpart). Additionally, satisfactory dopamine biosensing was accomplished for such TADF-Pdots/CO couple. All those results are combined to highlight the promising potential of such an aqueous TADF-ECL strategy.
为了实现最有效的全激子采集有机电致化学发光(ECL)用于生物传感,成功地推出了水相热激活延迟荧光(TADF)-ECL(水相 TADF-ECL),为水相荧光 ECL(水相 FL-ECL)的理论 ECL 效率限制提供了突破。然而,实现适用于水相 TADF-ECL 的高效 TADF 发射器仍然具有挑战性。以前的策略依赖于 TADF 小分子纳米粒子(NPs)。然而,这种 TADF 分子在 NPs 内的聚集猝灭非常强烈,使得这些 NPs 对 ECL 发射效率不高。在此,我们提出了开发基于共轭聚合物点(Pdots)的水相 TADF-ECL。与本征 TADF 聚合物相比,Pdots 在水中实现了可比的 TADF 光物理性质,例如,可比的 PL 光谱、相似的 PL 量子效率()和强烈的延迟荧光贡献,以及快速的反向系间交叉速率()为 1.5×10 s。所得氧化还原 ECL 体系(CO 作为共反应物)的相对 ECL 效率()高达 11.73%(Ru(bpy) 对应的)。此外,对于这种 TADF-Pdots/CO 偶联物,还完成了令人满意的多巴胺生物传感。所有这些结果都结合在一起,突出了这种水相 TADF-ECL 策略的有前途的潜力。