Department of Chemistry, National Tsing Hua University , No. 101, Sec. 2, Kuang-Fu Road, Hsinchu 30013, Taiwan.
ACS Appl Mater Interfaces. 2014;6(21):18824-31. doi: 10.1021/am504546f. Epub 2014 Oct 31.
This paper describes an eco-friendly, one-pot strategy for the synthesis of water-soluble, high-quantum-yield gold nanoclusters (AuNCs) stabilized with 11-mercaptoundecanoic acid (MUA) on their surfaces. The as-prepared ultrasmall MUA-AuNCs (1.9 nm) exhibited a quantum yield (QY) of 13%, higher than those of most previously described thiol-protected AuNCs. We applied these MUA-AuNCs as a versatile probe to develop a fluorescence "turn-off" assay for sensing Hg(2+) ions as well as a fluorescence "turn-on" assay for sensing biothiols. The former assay operated through aggregation-induced fluorescence quenching upon interaction of the MUA-AuNCs with Hg(2+) ions in a buffer containing 2,6-pyridinedicarboxylic acid (PDCA); this probe provided high sensitivity and remarkable selectivity over other selected metal ions with a limit of detection (LOD) for Hg(2+) ions of 450 pM and linearity from 2 to 50 nM. In the latter assay for biothiols [i.e., cysteine (Cys), homocysteine (Hcy), glutathione (GSH)], the fluorescence of the Hg(2+)-MUA-AuNCs complexes was turned on because the affinity of Hg(2+) ions toward the SH group of the biothiols was greater than that toward the COOH groups of the MUA units on the surface of the AuNCs. This assay provided good linearity for the tested biothiols, ranging from 10 to 100 nM for Cys, from 10 to 100 nM for Hcy, and from 5 to 75 nM for GSH, with LODs of 5.4, 4.2, and 2.1 nM, respectively. In addition, these environmentally and biologically friendly AuNC probes tested satisfactorily against interference from a range of amino acids.
本文描述了一种绿色环保、一锅法策略,用于合成表面稳定有 11-巯基十一酸(MUA)的水溶性、高荧光量子产率的金纳米簇(AuNCs)。所制备的超小尺寸的 MUA-AuNCs(1.9nm)的荧光量子产率(QY)为 13%,高于大多数之前报道的硫醇保护的 AuNCs。我们将这些 MUA-AuNCs 用作一种多功能探针,开发了一种用于检测 Hg(2+)离子的荧光“关闭”测定法,以及一种用于检测生物硫醇的荧光“开启”测定法。前者的测定法是通过在含有 2,6-吡啶二甲酸(PDCA)的缓冲液中,MUA-AuNCs 与 Hg(2+)离子相互作用,引发聚集诱导荧光猝灭来实现的;该探针对 Hg(2+)离子具有高灵敏度和显著的选择性,检测限(LOD)为 450pM,线性范围为 2 至 50nM。在用于生物硫醇[即半胱氨酸(Cys)、同型半胱氨酸(Hcy)、谷胱甘肽(GSH)]的后者测定法中,由于 Hg(2+)离子与生物硫醇的 SH 基团的亲和力大于与 AuNCs 表面的 MUA 单元的 COOH 基团的亲和力,因此 Hg(2+)-MUA-AuNCs 配合物的荧光被打开。该测定法对所测试的生物硫醇具有良好的线性关系,Cys 的范围为 10 至 100nM,Hcy 的范围为 10 至 100nM,GSH 的范围为 5 至 75nM,检测限分别为 5.4、4.2 和 2.1nM。此外,这些环境友好且生物相容的 AuNC 探针在对抗一系列氨基酸的干扰时表现良好。