Guo Fanfan, Hu Yuanyuan, Zhou Huiwen, Li Yuanjin, Li Jiadi, Wei Guichuan, Han Jing Long, Gao Wenyue, He Sisi, Niu Wenxin, Zhang Ling
School of Science, Harbin Institute of Technology, Shenzhen, 518055, China.
School of Pharmacy, Gannan Medical University, Ganzhou, 314000, China.
Anal Chim Acta. 2025 Oct 15;1371:344441. doi: 10.1016/j.aca.2025.344441. Epub 2025 Jul 17.
NIR-I electrochemiluminescence (ECL) is emerging as highly sensitive detection strategy due to its low background at the ambient conditions. Nonetheless, the applications of current NIR-I ECL nanoprobes are limited to the harsh synthetic/testing condition, high toxicity, low signal, and poor biocompatibility. In this study, glutathione/lipoic acid-protected trimetallic AuPtAg nanoclusters (GSH/LA/AuPtAg NCs) are demonstrated as an efficient nanoprobe with strong ECL signals around 850 nm in the presences of triethylamine. Critically, the alloying of Ag into the bimetallic Au Pt NCs altered the electronic structures of Pt(II), valences of Au(0), and the zata potentials of NCs, promoting the ECL intensities at 850 nm by 1.0 time. Additionally, the partly ligand-exchange of GSH by LA further increased the ECL intensities at 850 nm by 2.2 times through accelerating electron transfer processes. Meanwhile, the NIR-I fluorescence (λ = 910 nm) was enhanced. More importantly, the utilization of GSH/LA/AuPtAg NCs μg is enhanced by 3000 times after embedding into SiO microspheres (D, 318 nm). Because noradrenalin has substantial inhibition effects to NIR-I ECL of GSH/LA/AuPtAg/SiO, 1.0 nM-0.1 mM noradrenalin was detected with the low limit of detection as 0.04 nM (S/N = 3) selectively. Biomolecules, glucose, ascorbic acid, or uric acid didn't interrupt the detection of noradrenalin. The sensitivity of this ECL method to detect noradrenalin is much higher than those in previous reports, enabling the early diagnosis of neurogenic diseases.
近红外一区电化学发光(ECL)由于在环境条件下背景低,正成为一种高灵敏度的检测策略。然而,目前的近红外一区ECL纳米探针的应用局限于苛刻的合成/测试条件、高毒性、低信号和生物相容性差。在本研究中,谷胱甘肽/硫辛酸保护的三金属AuPtAg纳米簇(GSH/LA/AuPtAg NCs)被证明是一种高效的纳米探针,在三乙胺存在下,在850 nm左右具有很强的ECL信号。至关重要的是,将Ag合金化到双金属AuPt NCs中改变了Pt(II)的电子结构、Au(0)的价态以及NCs的zeta电位,使850 nm处的ECL强度提高了1.0倍。此外,LA对GSH的部分配体交换通过加速电子转移过程,使850 nm处的ECL强度进一步提高了2.2倍。同时,近红外一区荧光(λ = 910 nm)增强。更重要的是,嵌入SiO微球(D,318 nm)后,GSH/LA/AuPtAg NCs的利用率提高了3000倍。由于去甲肾上腺素对GSH/LA/AuPtAg/SiO的近红外一区ECL有显著抑制作用,因此能够以0.04 nM(S/N = 3)的低检测限选择性地检测1.0 nM - 0.1 mM的去甲肾上腺素。生物分子、葡萄糖、抗坏血酸或尿酸不会干扰去甲肾上腺素的检测。这种ECL方法检测去甲肾上腺素的灵敏度远高于以往报道,能够实现神经源性疾病的早期诊断。