Lab of Biochemical Sensing Technology, School of Chemistry and Molecular Engineering, Shanghai Key Laboratory for Urban Ecological Processes and Eco-Restoration , East China Normal University , 500 Dongchuan Road , Shanghai 200241 , China.
Anal Chem. 2018 Mar 6;90(5):3443-3451. doi: 10.1021/acs.analchem.7b05167. Epub 2018 Feb 19.
Recent years have witnessed the rapid development of pattern-based sensors due to their potential to detect and differentiate a wealth of analytes with only few probes. However, no one has found or used the combination of DNA and terbium(III) (Tb) as a pattern recognition system for large-scale mix-and-measure assays. Here we report for the first time that DNA-sensitized Tb (DNA/Tb), as a label-free and versatile "chemical nose/tongue", can be employed for wide-scale time-gated luminescent (TGL) monitoring of metal ions covering nearly the entire periodic table in a cost-effective fashion. A series of guanine/thymine (G/T)-rich DNA ligands was screened to sensitize the luminescence of Tb (referring to the antenna effect) as smart pattern responders to metal ions in solution, and metal ion-DNA interactions can differentially alter the antenna effect of DNA toward Tb as pattern signals. Our results show that as few as 3 DNA/Tb label-free sensors could successfully discriminate 49 analytes, including alkali-metal ions, alkaline-earth-metal ions, transition/post-transition metal ions, and lanthanide ions. A blind test with 49 metals further confirmed the discriminating power of DNA/Tb sensors. Moreover, the lifetime-based pattern recognition application using DNA/Tb sensors was also demonstrated. This DNA/Tb pattern recognition strategy could be extended to construct a series of "chemical noses/tongues" for monitoring various biochemical species by using different responsive DNA ligands, thus promising a versatile and powerful tool for a sensing application and investigation of DNA-involving molecular interactions.
近年来，基于模式的传感器由于其具有仅用少数探针就能检测和区分大量分析物的潜力，因此得到了迅猛的发展。然而，还没有人发现或使用 DNA 和铽(III)（Tb）的组合作为用于大规模混合和测量分析的模式识别系统。在这里，我们首次报道，DNA 敏化的铽（DNA/Tb）作为一种无标记且多功能的“化学鼻/舌”，可以用于以具有成本效益的方式广泛监测涵盖整个元素周期表的金属离子的宽范围时间门控发光（TGL）。筛选了一系列富含鸟嘌呤/胸腺嘧啶（G/T）的 DNA 配体来敏化 Tb 的发光（称为天线效应），作为溶液中金属离子的智能模式响应体，并且金属离子-DNA 相互作用可以不同地改变 DNA 对 Tb 的天线效应作为模式信号。我们的结果表明，仅使用 3 个无标记的 DNA/Tb 传感器即可成功区分 49 种分析物，包括碱金属离子、碱土金属离子、过渡/后过渡金属离子和镧系元素离子。对 49 种金属的盲测进一步证实了 DNA/Tb 传感器的区分能力。此外，还展示了使用 DNA/Tb 传感器进行基于寿命的模式识别应用。这种 DNA/Tb 模式识别策略可以通过使用不同的响应性 DNA 配体扩展为构建一系列“化学鼻/舌”，从而有望成为用于监测各种生化物质的多功能强大工具，并研究涉及 DNA 的分子相互作用。
