Laboratory of Chemical Biology, Division of Biological Inorganic Chemistry, State Key Laboratory of Rare Earth Resource Utilization, Graduate School of the Chinese Academy of Sciences, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, China.
Chemistry. 2010 Jul 19;16(27):8147-54. doi: 10.1002/chem.201000306.
Here we report a reusable DNA single-walled carbon nanotube (SWNT)-based fluorescent sensor for highly sensitive and selective detection of Ag(+) and cysteine (Cys) in aqueous solution. SWNTs can effectively quench the fluorescence of dye-labeled single-stranded DNA due to their strong pi-pi stacking interactions. However, upon incubation with Ag(+), Ag(+) can induce stable duplex formation mediated by C-Ag(+)-C (C=cytosine) coordination chemistry, which has been further confirmed by DNA melting studies. This weakens the interactions between DNA and SWNTs, and thus activates the sensor fluorescence. On the other hand, because Cys is a strong Ag(+) binder, it can remove Ag(+) from C-Ag(+)-C base pairs and deactivates the sensor fluorescence by rewrapping the dye-labeled oligonucleotides around the SWNT. In this way, the fluorescence signal-on and signal-off of a DNA/SWNT sensor can be used to detect aqueous Ag(+) and Cys, respectively. This sensing platform exhibits high sensitivity and selectivity toward Ag(+) and Cys versus other metal ions and the other 19 natural amino acids, with a limit of detection of 1 nM for Ag(+) and 9.5 nM for Cys. Based on these results, we have constructed a reusable fluorescent sensor by using the covalent-linked SWNT-DNA conjugates according to the same sensing mechanism. There is no report on the use of SWNT-DNA assays for the detection of Ag(+) and Cys. This assay is simple, effective, and reusable, and can in principle be used to detect other metal ions by substituting C-C base pairs with other native or artificial bases that selectively bind to other metal ions.
在这里,我们报告了一种可重复使用的基于 DNA 单壁碳纳米管 (SWNT) 的荧光传感器,用于在水溶液中对 Ag(+) 和半胱氨酸 (Cys) 进行高灵敏度和选择性检测。SWNTs 可以由于其强的 π-π 堆积相互作用而有效地猝灭染料标记的单链 DNA 的荧光。然而,在与 Ag(+) 孵育时,Ag(+) 可以通过 C-Ag(+)-C(C=胞嘧啶)配位化学介导的稳定双链体形成,这一点已通过 DNA 熔解研究进一步证实。这削弱了 DNA 与 SWNTs 之间的相互作用,从而激活了传感器的荧光。另一方面,由于 Cys 是一种强的 Ag(+) 结合剂,它可以从 C-Ag(+)-C 碱基对中去除 Ag(+),并通过将染料标记的寡核苷酸重新包裹在 SWNT 周围来使传感器荧光失活。通过这种方式,DNA/SWNT 传感器的荧光信号 ON 和 OFF 可分别用于检测水溶液中的 Ag(+) 和 Cys。与其他金属离子和其他 19 种天然氨基酸相比,该传感平台对 Ag(+) 和 Cys 具有高灵敏度和选择性,其对 Ag(+) 的检测限为 1 nM,对 Cys 的检测限为 9.5 nM。基于这些结果,我们根据相同的传感机制,使用共价键合的 SWNT-DNA 缀合物构建了一种可重复使用的荧光传感器。尚未有关于使用 SWNT-DNA 测定法检测 Ag(+) 和 Cys 的报道。该测定法简单、有效且可重复使用,并且原则上可以通过用其他选择性结合其他金属离子的天然或人工碱基替代 C-C 碱基对,用于检测其他金属离子。