Long living excited state of protonated adenosine unveiled by ultrafast fluorescence spectroscopy and density functional theoretical study

Ruth Chau Ting Chan, Chris Tsz Leung Chan, Chensheng Ma (Corresponding Author), Kang Yi Gu, Han Xin Xie, Allen Ka Wa Wong, Qing Wu Xiong, Ming Liang Wang, Wai Ming Kwok (Corresponding Author)

Research output: Journal article publicationJournal articleAcademic researchpeer-review

Abstract

Adenosine (Ado) possesses ultrafast nonradiative dynamics accounting for its remarkably high photostability. The deactivation dynamics of Ado after protonation in an aqueous solution remains an elusive issue. Herein we report an investigation of the excited state dynamics of protonated Ado (AdoH+) performed using ultrafast time-resolved fluorescence spectroscopy combined with density functional theoretical calculation. The result obtained from comparison of conformers with protonation at different sites revealed that thesyn-conformer with protonation occurring at the N3 position (syn-N3) is the predominant form of AdoH+in the ground state, similar to that of Ado. In contrast, the fluorescence of AdoH+with maximum intensity at 385 nm, significantly red-shifted from that of Ado, displaying decay dynamics composed of an ultrafast component with the lifetime of ∼0.5 ps and a slower one of ∼2.9 ns. The former is because of the decay of thesyn-N3 conformer, similar to that reported for AdoH+under the gas phase condition. The latter is due to thesyn-N1 conformer formedviaultrafast proton transfer of thesyn-N3. The excited state ofsyn-N1 has a peculiar nonplanar conformation over the purine molecule, which is responsible for the substantial Stokes shift showed in the fluorescence spectrum and correlates with a large energy barrier for nonradiative decay likely involving a reversed proton transfer. This study demonstrates the importance of protonation and solvent environment in altering dramatically the excited states of Ado, providing insight for better understanding nonradiative dynamics of both the monomeric bases and the oligomeric or polymeric DNAs.

Original languageEnglish
Pages (from-to)6472-6480
Number of pages9
JournalPhysical Chemistry Chemical Physics
Volume23
Issue number11
DOIs
Publication statusPublished - 21 Mar 2021

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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