State Key Laboratory for Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. China.
Anal Chem. 2012 Mar 6;84(5):2124-8. doi: 10.1021/ac300005f. Epub 2012 Feb 22.
It is well-known that Zr(4+) could selectively bind with two phosphate-functionalized molecules through a coordinate covalent interaction to form a sandwich-structured complex (-PO(3)(2-)-Zr(4+)-PO(3)(2-)-). In this paper, we for the first time converted such interaction into fluorescence sensing systems for Zr(4+) via a target-triggered DNA molecular beacon strategy. In the new designed sensing system, two phosphorylated and pyrene-labeled oligonucleotides were chosen as both recognition and reporter units, which will be linked by target Zr(4+) to form a hairpin structure and bring the two labeled pyrene molecules into close proximity, resulting in a "turn-on" excimer fluorescence signal. Moreover, γ-cyclodextrin was introduced to afford an amplified fluorescence signal and, therefore, provided an improved sensitivity for the target Zr(4+). This allows detection of Zr(4+) with high sensitivity (limit of detection, LOD = 200 nM) and excellent selectivity. The proposed sensing system has also been used for detection of Zr(4+) in river water samples with satisfactory result.
众所周知,Zr(4+) 可以通过配位共价相互作用选择性地与两个磷酸基化分子结合,形成夹心结构的配合物(-PO(3)(2-)-Zr(4+)-PO(3)(2-)-)。在本文中,我们首次通过靶触发 DNA 分子信标策略将这种相互作用转化为用于 Zr(4+) 的荧光传感系统。在新设计的传感系统中,选择两个磷酸化和芘标记的寡核苷酸作为识别和报告单元,它们将被靶 Zr(4+) 连接形成发夹结构,并使两个标记的芘分子靠近,从而产生“开启”的激基荧光信号。此外,引入 γ-环糊精可提供放大的荧光信号,从而提高了对靶 Zr(4+) 的灵敏度。这使得可以高灵敏度(检测限,LOD = 200 nM)和优异的选择性检测 Zr(4+)。该传感系统还用于河水样品中 Zr(4+) 的检测,结果令人满意。