Higher-order human telomeric G-quadruplex DNA metalloenzymes enhance enantioselectivity in the Diels-Alder reaction.
Yinghao Li, Guoqing Jia, Changhao Wang, Mingpan Cheng, and Can Li
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Y. Li,+ Dr. G. Jia,+ Dr. C. Wang, M. Cheng, Prof. Dr. C. Li
State Key Laboratory of Catalysis
Dalian Institute of Chemical Physics, Chinese Academy of Sciences 457 Zhongshan Road, Dalian, 116023 (China)
E-mail: canli@dicp.ac.cn
- Y. Li,+ Dr. C. Wang, M. Cheng
University of Chinese Academy of Sciences No.19A Yuquan Road, Beijing, 100049 (China)
http://onlinelibrary.wiley.com/doi/10.1002/cbic.201402692/abstract;jsessionid=A689CBBF8B4ED7ED16035D8B729D4220.f01t04
http://onlinelibrary.wiley.com/doi/10.1002/cbic.201402692/epdf
Abstract
Short human telomeric (HT) DNA sequences form single G-quadruplex (G4) units and exhibit structure-based stereocontrol for a series of reactions. However, for more biologically relevant higher-order HT G4-DNAs (beyond a single G4 unit), the catalytic performances are unknown. Here, we found that higher-order HT G4-DNA copper metalloenzymes (two or three G4 units) afford remarkably higher enantioselectivity (>90 % ee) and a five- to sixfold rate increase, compared to a single G4 unit, for the Diels–Alder reaction. Electron paramagnetic resonance (EPR) and enzymatic kinetic studies revealed that the distinct catalytic function between single and higher-order G4-DNA copper metalloenzymes can be attributed to different CuII coordination environments and substrate specificity. Our finding suggests that, like protein enzymes and ribozymes, higher-order structural organization is crucial for G4-DNA-based catalysis.
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