Citation: Wang Yinghui, Jie Jialong, Zhao Hongmei, Bai Yu, Qin Peixuan, Song Di. Deprotonation of Guanine Radical Cation in G-Quadruplex: A Combined Experimental and Theoretical Study[J]. Acta Chimica Sinica, ;2018, 76(6): 475-482. doi: 10.6023/A17120557 shu

Deprotonation of Guanine Radical Cation in G-Quadruplex: A Combined Experimental and Theoretical Study

Wang Yinghui ^a,b ,
Jie Jialong ^a,b ,
Zhao Hongmei ^a,b ,
Bai Yu ^a ,
Qin Peixuan ^c ,
Song Di ^a,b,,

a.
Beijing National Laboratory for Molecular Science(BNLMS), Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
b.
University of Chinese Academy of Sciences, Beijing 100049
c.
Beijing Sanfan Middle School, Beijing 100088

Corresponding author: Song Di, songdi@iccas.ac.cn
Received Date: 27 December 2017
Available Online: 20 June 2018
Fund Project: the National Natural Science Foundation of China 91441108the National Natural Science Foundation of China 21773257Project supported by the National Natural Science Foundation of China (Nos. 21773257, 21373233 and 91441108)the National Natural Science Foundation of China 21373233

Figures(4)

G-Quadruplex can be a promising candidate as molecular electronic device due to the ability of transferring hole. Extensive studies have reported that fast deprotonation of guanine radical cation (G^·+) to form a neutral radical G(-H)^· is the most important reaction in competition with hole transfer in DNA, hindering potential applications of DNA in molecular electronics. We thus carry out joint experimental and theoretical studies on deprotonation of G^·+ in human telomere G-quadruplex AG₃(T₂AG₃)₃by using nanosecond laser flash photolysis and quantum chemical calculations. Upon 355 nm laser photolysis of Na₂S₂O₈, instantaneously generated SO₄^·- radical oxidizes G base in the G-quadruplex to G^·+. In the time-resolved absorption spectra that record the reaction of G-quadruplex with SO₄^·- at different temperatures, the transient absorptions of G(N(2)-H)^· featured by absorption band at 640 nm are observed. It turns out that the G-quadruplex deprotonation product is G(N(2)-H)^· and the deprotonation site is thereby validated to be amino proton. To obtain the activation energy of the G^·+ deprotonation in G-quadruplex, the N(2)-H deprotonation rate constants at different temperatures varying from 280 to 300 K in steps 5 K are measured at a high G-quadruplex concentration, where the deprotonation has been proved to be the rate-limiting step in our previous work. Based upon Arrhenius equation, the deprotonation activation energy of G^·+ in G-quadruplex is determined to be 20.0±1.0 kJ/mol. Further, the potential energy profile for the G^·+ deprotonation in G-quadruplex is calculated at M062X/6-31G(d) level by carefully taking into account hydration environment of G^·+ in G-quadruplex. The calculated energy barrier of 26.4 kJ/mol matches with the measured activation energy value, indicating the calculated potential energy profile can describe the deprotonation process of G^·+ in the G-quadruplex. These theoretical and experimental results provide valuable dynamics information and mechanistic insights for potential applications of DNA structures in electronic device.
- G-quadruplex,
- guanine radical cation,
- deprotonation reaction,
- activation energy,
- potential energy profile
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