School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
Anal Chem. 2022 Jun 21;94(24):8811-8817. doi: 10.1021/acs.analchem.2c01770. Epub 2022 Jun 8.
The photoluminescence, electroluminescence, and electrochemiluminescence from nanocrystals (NCs) have been extensively exploited for both fundamental and applied investigation over two decades, while the understanding of chemiluminescence (CL) from NCs is still far from clear by now. Herein, a general route for triggering CL from NC luminophore is proposed by extensively exploiting the charge transfer between n-type NCs and oxidants. Oxidants, such as KSO, HO, KMnO, and NaClO, can chemically inject the hole onto the valence band (VB) of methionine-capped n-type AuNCs (Met@AuNCs) and enable the occurrence of efficient radiative-charge-recombination between the chemically injected exogenous VB hole and the pre-existed endogenous conduction band (CB) electron, which eventually results in single-color and defect-involved CL with the maximum emission wavelength around 824 nm. The CL of Met@AuNCs/oxidant is qualified for ultrasensitive CL immunoassay in a similar procedure to the biotin-avidin and magnetic separation involved commercial CL immunoassay and exhibits acceptable performance for linearly determining carcinoembryonic antigen from 50 pg/mL to 100 ng/mL with a limit of detection of 10 pg/mL (S/N = 3). This strategy provides a general route to develop nanoparticulate CL luminophores and might eventually enable CL multiplexing assay via extensively exploiting the CL of different wavebands.
二十多年来,纳米晶体(NCs)的光致发光、电致发光和电致化学发光已被广泛用于基础研究和应用研究,而目前对 NCs 的化学发光(CL)的理解还远远不清楚。在此,通过广泛利用 n 型 NCs 与氧化剂之间的电荷转移,提出了一种触发 NC 发光体 CL 的通用方法。氧化剂(如 KSO、HO、KMnO 和 NaClO)可以将空穴化学注入到蛋氨酸封端的 n 型 AuNCs(Met@AuNCs)的价带(VB)中,并使化学注入的外来 VB 空穴与预存在的本征导带(CB)电子之间发生有效的辐射电荷复合,最终导致单色和涉及缺陷的 CL,最大发射波长约为 824nm。Met@AuNCs/氧化剂的 CL 适用于在类似于生物素-亲和素和磁分离的类似程序中的超灵敏 CL 免疫分析,并且可以线性地从 50pg/mL 到 100ng/mL 以 10pg/mL(S/N = 3)的检测限来检测癌胚抗原,表现出可接受的性能。该策略为开发纳米颗粒 CL 发光体提供了一种通用途径,并可能最终通过广泛利用不同波段的 CL 来实现 CL 多重分析。