Department of Applied Chemistry, National Chiao Tung University, Hsinchu 300, Taiwan.
Anal Chem. 2012 Jul 3;84(13):5484-8. doi: 10.1021/ac300332t. Epub 2012 Jun 11.
Glutathione-bound gold nanoclusters (AuNCs@GSH) can emit reddish photoluminescence under illumination of ultraviolet light. The luminescence of the AuNCs@GSH is quenched when chelating with iron ions (AuNCs@GSH-Fe(3+)), presumably resulting from the effective electron transfer between the nanoclusters and iron ions. Nevertheless, we found that the luminescence of the gold nanoclusters can be restored in the presence of phosphate-containing molecules, which suggested the possibility of using AuNCs@GSH-Fe(3+) complexes as the selective luminescent switches for phosphate-containing metabolites. Phosphate-containing metabolites such as adenosine-5'-triphosphate (ATP) and pyrophosphate play an important role in biological systems. In this study, we demonstrated that the luminescence of the AuNCs@GSH-Fe(3+) is switched-on when mixing with ATP and pyrophosphate, which can readily be observed by the naked eye. It results from the high formation constants between phosphates and iron ions. When employing fluorescence spectroscopy as the detection tool, quantitative analysis for phosphate-containing metabolites such as ATP and pyrophosphate can be conducted. The linear range for ATP and pyrophosphate is 50 μM to sub-millimolar, while the limit of detection for ATP and pyrophosphate are ∼43 and ∼28 μM, respectively. Additionally, we demonstrated that the luminescence of the AuNCs@GSH-Fe(3+) can also be turned on in the presence of phosphate-containing metabolites from cell lysates and blood plasma.
谷胱甘肽结合的金纳米团簇(AuNCs@GSH)在紫外光照射下会发出红色的光致发光。当与铁离子螯合时,AuNCs@GSH 的发光会被猝灭(AuNCs@GSH-Fe(3+)),这可能是由于纳米团簇和铁离子之间的有效电子转移。然而,我们发现,在含有磷酸盐的分子存在的情况下,金纳米团簇的发光可以恢复,这表明可以将 AuNCs@GSH-Fe(3+) 复合物用作含磷酸盐代谢物的选择性发光开关。含磷酸盐的代谢物,如腺苷-5'-三磷酸(ATP)和焦磷酸盐,在生物系统中起着重要作用。在本研究中,我们证明了当与 ATP 和焦磷酸盐混合时,AuNCs@GSH-Fe(3+) 的发光会被打开,这可以用肉眼轻易观察到。这是由于磷酸盐与铁离子之间的高形成常数所致。当使用荧光光谱作为检测工具时,可以对 ATP 和焦磷酸盐等含磷酸盐代谢物进行定量分析。对于 ATP 和焦磷酸盐,线性范围为 50 μM 至亚毫摩尔,而对于 ATP 和焦磷酸盐的检测限分别约为 43 和 28 μM。此外,我们还证明了在细胞裂解物和血浆中存在含磷酸盐的代谢物时,AuNCs@GSH-Fe(3+) 的发光也可以被打开。