CuII-mediated stabilisation of DNA duplexes bearing consecutive ethenoadenine lesions and its application to a metal-responsive DNAzyme

Silpa Chandran Rajasree; Yusuke Takezawa; Mitsuhiko Shionoya

doi:10.1039/d2cc06179a

Cu^II-mediated stabilisation of DNA duplexes bearing consecutive ethenoadenine lesions and its application to a metal-responsive DNAzyme

Chem Commun (Camb). 2023 Jan 24;59(8):1006-1009. doi: 10.1039/d2cc06179a.

Authors

Silpa Chandran Rajasree¹, Yusuke Takezawa¹, Mitsuhiko Shionoya¹

Affiliation

¹ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1, Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan. takezawa@chem.s.u-tokyo.ac.jp.

PMID: 36524578
DOI: 10.1039/d2cc06179a

Abstract

Metal-mediated nucleobase pairing can play a central role in the expression of metal-responsive DNA functions. We report the Cu^II-mediated stabilisation of DNA duplexes bearing damaged nucleobases, 1,N⁶-ethenoadenine (εA), as metal-binding sites, which was utilised to construct a metal-responsive DNAzyme. Consecutive incorporation of three or more εA-εA mismatch pairs allowed for Cu^II-dependent significant duplex stabilisation through metal-mediated εA-Cu^II-εA base pairing. Subsequently, a split DNAzyme with three εA-Cu^II-εA base pairs was strategically designed. The activity of the εA-modified DNAzyme was enhanced by 5.3-fold upon addition of Cu^II ions. This study demonstrates the utility of εA lesions for building metal-responsive DNA architectures.

MeSH terms

Adenine / chemistry
Base Pairing
DNA / chemistry
DNA, Catalytic* / metabolism
Metals / chemistry

Substances

DNA, Catalytic
Adenine
DNA
Metals