School of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, Japan.
Application, Bruker Japan K.K., 3-9 Moriya-cho, Kanagawa-ku, Yokohama, Kanagawa 221-0022, Japan.
Dalton Trans. 2021 Jun 8;50(22):7633-7639. doi: 10.1039/d1dt00975c.
The redox properties of metallo-base pairs remain to be elucidated. Herein, we report the detailed 1H/13C/109Ag NMR spectroscopic and cyclic voltammetric characterisation of the [Ag(cytidine)2]+ complex as isolated cytosine-Ag+-cytosine (C-Ag+-C) base pairs. We also performed comparative studies between cytidine/Ag+ and other nucleoside/Ag+ systems by using cyclic voltammetry measurements. In addition, to evaluate the effect of [Ag(cytidine)2]+ formation on the chemical reduction of Ag+ to Ag, we utilised the redox reaction between Ag+ and tetrathiafulvalene (TTF). We found that Ag+-mediated base pairing lowers the redox potential of the Ag+/Ag couple. In addition, C-Ag+-C base pairing makes it more difficult to reduce captured Ag+ ions than in other nucleoside/Ag+ systems. Remarkably, the cytidine/Ag+ system can be utilised to control the redox potential of the Ag+/Ag couple in DMSO. This feature of the cytidine/Ag+ system may be exploited for Ag nanoparticle synthesis by using the redox reaction between Ag+ and TTF.
金属碱基对的氧化还原性质仍有待阐明。在此，我们报道了孤立的胞嘧啶-银+-胞嘧啶（C-Ag+-C）碱基对中[Ag（胞嘧啶）2]+配合物的详细 1H/13C/109Ag NMR 光谱和循环伏安特性。我们还通过循环伏安法测量对胞嘧啶/Ag+和其他核苷/Ag+体系进行了比较研究。此外，为了评估[Ag（胞嘧啶）2]+形成对 Ag+化学还原为 Ag 的影响，我们利用了 Ag+和四硫富瓦烯（TTF）之间的氧化还原反应。我们发现 Ag+-介导的碱基配对降低了 Ag+/Ag 对的氧化还原电位。此外，与其他核苷/Ag+体系相比，C-Ag+-C 碱基配对使得捕获的 Ag+离子更难还原。值得注意的是，胞嘧啶/Ag+体系可用于控制 DMSO 中 Ag+/Ag 对的氧化还原电位。该胞嘧啶/Ag+体系的这一特性可用于通过 Ag+和 TTF 之间的氧化还原反应来合成 Ag 纳米粒子。
