4.8 Article

Insights into How NH4+Ions Enhance the Activity of Dimeric G-Quadruplex/Hemin DNAzyme

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ACS CATALYSIS
卷 13, 期 7, 页码 4330-4338

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AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c05905

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dimeric G-quadruplex; NH4+; DNAzyme; hemin; mechanism; enhancing activity

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In this study, the effect of NH4+ ions on the catalytic behavior of the dimeric G4/Hemin DNAzyme was investigated. It was found that NH4+ ions increased the accumulation of compound I (Cpd I) in the dimeric DNAzyme process. Molecular dynamics simulations showed that NH4+ ions could stabilize the dimeric G4 and interact with the substrate hydrogen peroxide through hydrogen bonds. The interaction between NH4+ ions and H2O2 contributed to the stability of intermediate and transition-state species involved in the catalytic formation of Cpd I.
Dimeric G-quadruplex (G4)/Hemin has been employed to expand the catalytic repertoire of nucleic acid. Herein, we aim to understand the effect of NH4+ ions on the catalytic behavior of the dimeric G4/Hemin DNAzyme. Through EPR and UV-vis spectroscopy, we found that NH4+ ions resulted in more accumulation of compound I (Cpd I, Fe (IV)=O center dot+) in the dimeric DNAzyme process. Furthermore, molecular dynamics simulations showed that NH4+ ions could be present in the catalytic chamber to stabilize the dimeric G4 while interacting with the substrate hydrogen peroxide by hydrogen bonds. The interaction between the NH4+ ion and H2O2 contributes to a better stability of intermediate and transition-state species involved in the catalytic formation of Cpd I. Specifically, NH4+ ions facilitate the O-O bond breaking of iron-porphyrin-bound H2O2 (the rate-limiting step). With four available hydrogen atoms, a NH4+ ion can be an effective additive to promote the activity of the dimeric DNAzyme. The results provide the strategy for adjusting the DNAzyme by transition-state stabilization by hydrogen bonding networks. Our data shed light on the mechanistic clues on the design and application of G4-based catalysts.

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