基于配体的屏蔽效应诱导金纳米团簇的高效近红外电化学发光及其传感应用,Analytical Chemistry

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基于配体的屏蔽效应诱导金纳米团簇的高效近红外电化学发光及其传感应用
Analytical Chemistry ( IF 6.7 ) Pub Date : 2023-04-20 , DOI: 10.1021/acs.analchem.2c04939
Yamin Nie _{1,

2} , Yue Zhang ₁ , Weiwei Cao ₁ , Ya-Qin Chai ₁ , Ruo Yuan ₁

Affiliation

由于共反应物自由基在水性介质中的稳定性差，制备高效 ECL 金纳米团簇 (Au NCs) 仍然面临着严峻的挑战。在此，我们报告了以三乙胺 (TEA) 作为共反应物的 β-环糊精保护的 Au NCs (β-CD-Au NCs) 的基于配体的屏蔽效应诱导记录的近红外 (λ _{max = 786 nm) ECL 效率。}具有匹配疏水空腔的β-CD-Au NCs 的配体可以封装由主客体化学驱动的TEA，这不仅允许TEA 在空腔中生成• 以减少环境暴露，从而减少溶解氧、水的^猝灭等，而且无需大量化学修饰即可缩短电荷转移路径。密度泛函理论，¹H NMR 光谱、电子顺磁共振和微分脉冲伏安法研究表明，基于 β-CD 配体的屏蔽效应显着提高了 TEA 的反应效率。更重要的是，与传统配体保护的 Au NCs 形成鲜明对比的是，β-CD-Au NCs 的 ECL 效率比 BSA-Au NCs 提高了 321 倍，比 ATT-Au NCs 提高了 153 倍，比 ATT-Au NCs 提高了 19 倍含 1 mM TEA 的 GSH-Au NC。因此，这项工作深入了解了配体在增强高效 ECL 金属 NC 的活性共反应物自由基稳定性方面的关键作用，从而极大地激发了它们的应用前景。使用 β-CD-Au NCs 作为发射器，构建了一个“信号关闭”ECL 传感平台，以检测去甲肾上腺素作为模型目标，检测下限为 0.91 nM。

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Ligand-Based Shielding Effect Induced Efficient Near-Infrared Electrochemiluminescence of Gold Nanoclusters and Its Sensing Application

Preparing high-efficiency ECL gold nanoclusters (Au NCs) still faces a serious challenge due to the poor stability of co-reactant radicals in aqueous media. Herein, we report a ligand-based shielding effect induced record near-infrared (λ_max = 786 nm) ECL efficiency of β-cyclodextrin-protected Au NCs (β-CD-Au NCs) with triethylamine (TEA) as co-reactant. The ligand of β-CD-Au NCs with a matched hydrophobic cavity could encapsulate TEA driven by host–guest chemistry, which not only allows the generation of TEA^• in the cavity to diminish environmental exposure, thus reducing the quenching by dissolved oxygen, water, etc., but also shortens the charge transfer pathway without extensive chemical modification. Density functional theory, ¹H NMR spectra, electron paramagnetic resonance, and differential pulse voltammetry studies revealed that the β-CD ligand-based shielding effect significantly increased the reactivity efficiency of TEA. More importantly, in stark contrast to those of traditional ligand-protected Au NCs, the ECL efficiency of β-CD-Au NCs enhanced 321-fold versus BSA-Au NCs, 153-fold versus ATT-Au NCs, and 19-fold versus GSH-Au NCs with 1 mM TEA. Therefore, this work provides an in-depth understanding of the crucial role of ligands in enhancing the active co-reactant radical stability for high-efficiency ECL metal NCs to immensely stimulate their promising applications. Using the β-CD-Au NCs as emitters, a “signal off” ECL sensing platform was constructed to detect noradrenaline as a model target with a lower detection limit of 0.91 nM.

更新日期：2023-04-20

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