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Article

Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study

Department of Chemistry, Durham University, Durham DH1 3LE, UK
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Author to whom correspondence should be addressed.
Academic Editors: Fatwa Firdaus Abdi and Danilo Roccatano
Molecules 2021, 26(10), 2877; https://doi.org/10.3390/molecules26102877
Received: 7 April 2021 / Revised: 5 May 2021 / Accepted: 10 May 2021 / Published: 13 May 2021
(This article belongs to the Special Issue Women in Physical Chemistry)
A carboxylated adenosine analog (C-Ado) has been synthesized and probed via time-resolved photoelectron spectroscopy in order to induce intra-molecular charge transfer from the carboxylic acid moiety to the nucleobase. Intra-molecular charge transfer can be exploited as starting point to probe low-energy electron (LEE) damage in DNA and its derivatives. Time-dependent density functional theory (TD-DFT) calculations at the B3LYP-6311G level of theory have been performed to verify that the highest occupied molecular orbital (HOMO) was located on carboxylic acid and that the lowest occupied molecular orbital (LUMO) was on the nucleobase. Hence, the carboxylic acid could work as electron source, whilst the nucleobase could serve the purpose of electron acceptor. The dynamics following excitation at 4.66 eV (266 nm) were probed using time-resolved photoelectron spectroscopy using probes at 1.55 eV (800 nm) and 3.10 eV (400 nm). The data show rapid decay of the excited state population and, based on the similarity of the overall dynamics to deoxy-adenosine monophosphate (dAMP), it appears that the dominant decay mechanism is internal conversion following 1ππ* excitation of the nucleobase, rather than charge-transfer from the carboxylic acid to the nucleobase. View Full-Text
Keywords: photoelectron spectroscopy; low energy electron damage in DNA; charge transfer photoelectron spectroscopy; low energy electron damage in DNA; charge transfer
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MDPI and ACS Style

Castellani, M.E.; Verlet, J.R.R. Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study. Molecules 2021, 26, 2877. https://doi.org/10.3390/molecules26102877

AMA Style

Castellani ME, Verlet JRR. Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study. Molecules. 2021; 26(10):2877. https://doi.org/10.3390/molecules26102877

Chicago/Turabian Style

Castellani, Maria E., and Jan R.R. Verlet. 2021. "Intramolecular Photo-Oxidation as a Potential Source to Probe Biological Electron Damage: A Carboxylated Adenosine Analogue as Case Study" Molecules 26, no. 10: 2877. https://doi.org/10.3390/molecules26102877

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