Wang Hao, Wang Yongxiang, Jin Jianyu, Yang Ronghua
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
Anal Chem. 2008 Dec 1;80(23):9021-8. doi: 10.1021/ac801382k.
An approach for visual and fluorescent sensing of Hg2+ in aqueous solution is presented. This method is based on the Hg(2+)-induced conformational change of a thymine (T)-rich single-stranded DNA (ssDNA) and the difference in electrostatic affinity between ssDNA and double-stranded (dsDNA) with gold nanoparticles. The dye-tagged ssDNA containing T-T mismatched sequences was chosen as Hg2+ acceptor. At high ionic strength, introduction of the ssDNA to a colloidal solution of the aggregates of gold nanoparticles results in color change, from blue-gray to red of the solution, and the fluorescence quenching of the dye. Binding of Hg2+ with the ssDNA forms the double-stranded structure. This formation of dsDNA reduces the capability to stabilize bare nanoparticles against salt-induced aggregation, remaining a blue-gray in the color of the solution, but fluorescence signal enhancement compared with that without Hg2+. With the optimum conditions described, the system exhibits a dynamic response range for Hg2+ from 9.6 x 10(-8) to 6.4 x 10(-6) M with a detection limit of 4.0 x 10(-8) M. Both the color and fluorescence changes of the system are extremely specific for Hg2+ even in the presence of high concentrations of other heavy and transition metal ions, which meet the selective requirements for biomedical and environmental application. The combined data from transmission electron microscopy, fluorescence anisotropy measurements, and dialysis experiments indicate that both the color and the fluorescence emission changes of the DNA-functioned gold nanoparticles generated by Hg2+ are the results of the metal-induced formation of dsDNA and subsequent formation of nanoparticle aggregates.
本文提出了一种用于水溶液中Hg2+可视化和荧光传感的方法。该方法基于Hg(2+)诱导的富含胸腺嘧啶(T)的单链DNA(ssDNA)构象变化以及ssDNA与带有金纳米颗粒的双链(dsDNA)之间静电亲和力的差异。选择含有T-T错配序列的染料标记ssDNA作为Hg2+受体。在高离子强度下,将ssDNA引入金纳米颗粒聚集体的胶体溶液中会导致溶液颜色从蓝灰色变为红色,并使染料的荧光猝灭。Hg2+与ssDNA结合形成双链结构。dsDNA的这种形成降低了稳定裸纳米颗粒抵抗盐诱导聚集的能力,溶液颜色仍为蓝灰色,但与没有Hg2+时相比荧光信号增强。在所描述的最佳条件下,该系统对Hg2+的动态响应范围为9.6×10(-8)至6.4×10(-6)M,检测限为4.0×10(-8)M。即使在存在高浓度其他重金属和过渡金属离子的情况下,该系统的颜色和荧光变化对Hg2+也具有极高的特异性,满足生物医学和环境应用的选择性要求。来自透射电子显微镜、荧光各向异性测量和透析实验的综合数据表明,Hg2+产生的DNA功能化金纳米颗粒的颜色和荧光发射变化都是金属诱导的dsDNA形成以及随后纳米颗粒聚集体形成的结果。