Medical School, Institute of Reproductive Medicine, Nantong University, Nantong Jiangsu, 226001 China.
Langmuir. 2020 Nov 24;36(46):13928-13936. doi: 10.1021/acs.langmuir.0c02396. Epub 2020 Nov 11.
Glycine is the simplest amino acid in living organisms and plays important roles in biology and medicine. However, few biosensors for glycine sensing have been reported. Herein, we present a facile strategy to construct dopamine-modified AuCu bimetallic nanoclusters (denoted as AuCu NC-DA) as charge transfer-based biosensors for highly sensitive glycine sensing. The AuCu NCs stabilized by bovine serum albumin (BSA) exhibited a fluorescence maximum at 400 nm. Because of the high affinity of BSA for dopamine (DA), the surface of the AuCu NCs was modified with DA without any complicated chemical reactions, resulting in fluorescence quenching through a charge transfer process. Among 20 amino acids, AuCu NC-DA exhibited an off/on fluorescence switching response specifically toward glycine through the formation of hydrogen bonds with oxidized DA, which inhibited the charge transfer process, leading to the emergence of a new emission peak at 475 nm. Spectroscopic and thermodynamic results combined with molecular docking analyses provided comprehensive understanding of the sensing mechanism. Furthermore, we showed that AuCu NC-DA was able to sense glycine in cells by imaging. Finally, the practicability of AuCu NC-DA for glycine detection was validated in milk drink samples. This study presents a promising type of a charge transfer-based sensor.
甘氨酸是生物体内最简单的氨基酸,在生物学和医学中发挥着重要作用。然而,用于甘氨酸传感的生物传感器却很少有报道。在此,我们提出了一种简便的策略,构建了多巴胺修饰的 AuCu 双金属纳米团簇(记为 AuCu NC-DA),作为基于电荷转移的生物传感器,用于高灵敏度的甘氨酸传感。由牛血清白蛋白(BSA)稳定的 AuCu NCs 在 400nm 处表现出最大荧光。由于 BSA 与多巴胺(DA)具有高亲和力,AuCu NCs 的表面通过简单的非共价作用修饰上了 DA,导致通过电荷转移过程发生荧光猝灭。在 20 种氨基酸中,AuCu NC-DA 通过与氧化 DA 形成氢键特异性地对甘氨酸表现出开/关荧光切换响应,抑制了电荷转移过程,从而在 475nm 处出现新的发射峰。光谱和热力学结果结合分子对接分析提供了对传感机制的全面理解。此外,我们通过成像展示了 AuCu NC-DA 能够在细胞中检测甘氨酸。最后,在牛奶饮料样品中验证了 AuCu NC-DA 用于检测甘氨酸的实用性。这项研究提出了一种有前景的基于电荷转移的传感器。