Effect of cytosine-Ag+-cytosine base pairing on the redox potential of the Ag+/Ag couple and the chemical reduction of Ag+ to Ag by tetrathiafulvalene

Takenori Dairaku; Rika Kawai; Teppei Kanaba; Tetsuya Ono; Kentaro Yoshida; Hajime Sato; Kanako Nozawa-Kumada; Yoshinori Kondo; Jiro Kondo; Akira Ono; Yoshiyuki Tanaka; Yoshitomo Kashiwagi

doi:10.1039/d1dt00975c

Effect of cytosine-Ag⁺-cytosine base pairing on the redox potential of the Ag⁺/Ag couple and the chemical reduction of Ag⁺ to Ag by tetrathiafulvalene

Dalton Trans. 2021 Jun 8;50(22):7633-7639. doi: 10.1039/d1dt00975c.

Authors

Affiliations

¹ School of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima 963-8611, Japan. t-dairaku@pha.ohu-u.ac.jp y-kashiwagi@pha.ohu-u.ac.jp.
² Application, Bruker Japan K.K., 3-9 Moriya-cho, Kanagawa-ku, Yokohama, Kanagawa 221-0022, Japan.
³ Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai, Miyagi 980-8578, Japan.
⁴ Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan.
⁵ Department of Material & Life Chemistry, Faculty of Engineering, Kangawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, Kanagawa 221-8686, Japan.
⁶ Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan. tanakay@ph.bunri-u.ac.jp.

PMID: 33973617
DOI: 10.1039/d1dt00975c

Abstract

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.