期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 59, 期 9, 页码 3444-3449出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201912962
关键词
artificial metalloribozymes; c-di-AMP; cyclic dinucleotides; homogeneous catalysis; nucleic acid based catalysts
资金
- National Natural Science Foundation of China [21703132, 21773149, 21273142]
- Natural Science Foundation of Shaanxi Province of China [2019JQ161]
- Fundamental Research Funds for the Central Universities [GK201802001]
The diverse secondary structures of nucleic acids are emerging as attractive chiral scaffolds to construct artificial metalloenzymes (ArMs) for enantioselective catalysis. DNA-based ArMs containing duplex and G-quadruplex scaffolds have been widely investigated, yet RNA-based ArMs are scarce. Here we report that a cyclic dinucleotide of c-di-AMP and Cu2+ ions assemble into an artificial metalloribozyme (c-di-AMP.Cu2+) that enables catalysis of enantioselective Friedel-Crafts reactions in aqueous media with high reactivity and excellent enantioselectivity of up to 97 % ee. The assembly of c-di-AMP.Cu2+ gives rise to a 20-fold rate acceleration compared to Cu2+ ions. Based on various biophysical techniques and density function theory (DFT) calculations, a fine coordination structure of c-di-AMP.Cu2+ metalloribozyme is suggested in which two c-di-AMP form a dimer scaffold and the Cu2+ ion is located in the center of an adenine-adenine plane through binding to two N7 nitrogen atoms and one phosphate oxygen atom.
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