Citation: Yan Guo, Hongtao Bian, Le Yu, Jiani Ma, Yu Fang. Photochemical reaction mechanism of benzophenone protected guanosine at N7 position[J]. Chinese Chemical Letters, ;2025, 36(3): 109971. doi: 10.1016/j.cclet.2024.109971 shu

Photochemical reaction mechanism of benzophenone protected guanosine at N7 position

Yan Guo ^a ,
Hongtao Bian ^a ,
Le Yu ^b ,
Jiani Ma ^{a, *,} ,
Yu Fang ^a

a.
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China
b.
Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710127, China

majiani@snnu.edu.cn

Received Date: 29 February 2024
Revised Date: 23 April 2024
Accepted Date: 7 May 2024
Available Online: 8 May 2024

Figures(8)

Aryl ketones as photolabile protecting group (PPG) to modify purine imines is a novel nucleic acid protection strategy. Especially, photoprotection of N7-guanosine is the first reported photoprotected nucleoside that can affect the Hoogsteen recognition site of guanosine. However, the mechanism, which is pivotal to high efficiency of photorelease and applications of PPGs in biological and medical systems, is unclear. Here, a detailed deprotection mechanism of benzophenone protected guanosine (BP-Guo) at N7 position is reported. Upon irradiation, BP-Guo populates to singlet state, which generates ³[BP]-Guo via intersystem crossing process. Thereafter, triplet energy transfer competes with hydrogen atom transfer forming BP-³[Guo] and ketyl-Guo, respectively. Both species break CN bond to release guanosine. These results provide deeper insights into exploiting improved strategies for photo-protecting nucleic acids. In particular, the TTET pathway could trigger well-known cyclization reactions that brings about DNA mutagenic adducts. The latter should be avoided in developing improved strategies for photoprotecting nucleic acids.
- Excited state,
- Photolabile protecting group,
- Time-resolved spectroscopy,
- Transient absorption,
- DFT calculation
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