Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest University), Ministry of Education, School of Chemistry and Chemical Engineering , Southwest University , Chongqing 400715 , China.
Laboratory of Environment Change and Ecological Construction of Hebei Province, College of Resources and Environment Science , Hebei Normal University , Shijiazhuang , Hebei 050024 , China.
Anal Chem. 2020 Feb 18;92(4):3324-3331. doi: 10.1021/acs.analchem.9b05262. Epub 2020 Jan 28.
The design and exploration of highly efficient organic luminophores for an electrochemiluminescence (ECL) sensor is a fascinating and promising subject. Herein, we present a surfactant-assisted self-assembly of 5,10,15,20-tetrakis (4-carboxyphenyl) porphyrin (TCPP) J-aggregate as a robust organic luminophore to construct the solid-state ECL sensing platform with significantly enhanced and constantly stable signals, by using peroxydisulfate (SO) as the coreactant, and l-cysteine capped zinc oxide nanoflowers (ZnO@Cys NFs) as the multifunctional energy donor and coreactant accelerator. Compared with TCPP monomer, this TCPP J-aggregate possesses a unique aggregation-induced electrochemiluminescence (AIECL) performance, which results in 5-fold enhancement in red-light ECL emission at 675 nm. The resonance energy transfer from the ZnO@Cys NFs (energy donor) to the TCPP J-aggregate (energy acceptor) substantially improves the ECL intensity and stability. ZnO@Cys NFs have also been used as a coreactant accelerator to promote the conversion of more SO into SO. The corresponding ECL mechanism has been investigated by UV-vis absorption spectrum, photoluminescence, ECL, and density functional theory. Since l-cysteine on ZnO@Cys NFs can efficiently realize bidentate chelation with Cu, the proposed ECL sensor shows a highly selective and sensitive quenching effect for the detection of Cu with a wide linear range from 1.0 pmol·L to 500 nmol·L and a detection limit of 0.33 pmol·L, paving a bright research direction for the development of TCPP aggregates in ECL field.
本文提出了一种基于表面活性剂辅助的 5,10,15,20-四(4-羧基苯基)卟啉(TCPP)J-聚集体的自组装策略，将其作为一种稳健的有机发光体，构建了固态电化学发光(ECL)传感平台，该平台具有显著增强且稳定的信号，其中过二硫酸盐(SO)作为共反应物，l-半胱氨酸封端的氧化锌纳米花(ZnO@Cys NFs)作为多功能能量供体和共反应物加速剂。与 TCPP 单体相比，该 TCPP J-聚集体具有独特的聚集诱导电化学发光(AIECL)性能，在 675nm 处红光 ECL 发射强度增强了 5 倍。ZnO@Cys NFs 的共振能量转移(从能量供体到能量受体)极大地提高了 ECL 的强度和稳定性。ZnO@Cys NFs 还可用作共反应物加速剂，以促进更多 SO转化为 SO。通过紫外-可见吸收光谱、光致发光、ECL 和密度泛函理论研究了相应的 ECL 机制。由于 ZnO@Cys NFs 上的 l-半胱氨酸可以有效地实现与 Cu 的双齿螯合，因此所提出的 ECL 传感器对 Cu 的检测表现出高度选择性和灵敏的猝灭效应，线性范围从 1.0pmol·L到 500nmol·L，检测限为 0.33pmol·L，为 TCPP 聚集体在 ECL 领域的发展开辟了一个光明的研究方向。
