Premium
Sharp Switching of DNAzyme Activity through the Formation of a Cu II ‐Mediated Carboxyimidazole Base Pair
Author(s) -
Takezawa Yusuke,
Hu Lingyun,
Nakama Takahiro,
Shionoya Mitsuhiko
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202009579
Subject(s) - deoxyribozyme , chemistry , dna , base pair , cleavage (geology) , substrate (aquarium) , crystallography , ion , stereochemistry , biochemistry , materials science , biology , ecology , organic chemistry , fracture (geology) , composite material
Abstract DNAzymes are widely used as functional units for creating DNA‐based sensors and devices. Switching of DNAzyme activity by external stimuli is of increasing interest. Herein we report a Cu II ‐responsive DNAzyme rationally designed by incorporating one of the most stabilizing artificial metallo‐base pairs, a Cu II ‐mediated carboxyimidazole base pair (Im C ‐Cu II ‐Im C ), into a known RNA‐cleaving DNAzyme. Cleavage of the substrate was suppressed without Cu II , but the reaction proceeded efficiently in the presence of Cu II ions. This is due to the induction of a catalytically active structure by Im C ‐Cu II ‐Im C pairing. The on/off ratio was as high as 12‐fold, which far exceeds that of the previously reported DNAzyme with a Cu II ‐mediated hydroxypyridone base pair. The DNAzyme activity can be regulated specifically in response to Cu II ions during the reaction through the addition, removal, or reduction of Cu II . This approach should advance the development of stimuli‐responsive DNA systems with a well‐defined sharp switching function.