Benzo[a]pyrene is a carcinogenic polyaromatic hydrocarbon, which can react with DNA causing mutations and, eventually, cancer. The fluorescent property of benzo[a]pyrene is an important characteristic which has been widely used in biochemical applications. This study focuses on computational simulations of a set of synthetically modified nucleotides originated from benzo[a]pyrene. In this work, we apply classical force field dynamics and <i>ab initio</i> Born-Oppenheimer molecular dynamics calculations in explicit solvent to investigate the ground and excited state surfaces of this set of molecules. Our simulations probe how changing the nucleobase next to benzo[a]pyrene and modifications of the pyrene group by adding functional groups affects the excited state dynamics. We show that the emission spectrum redshifts when benzo[a]pyrene is functionalized with highly electronegative groups, and is slightly blue shifted with more neutral groups. We also demonstrate the effect of purine vs pyrimidine nucleobases on the accessibility of particular excited states. This study gives atomistic and electronic insight into the relatively fast excited state dynamics of these systems, and provides new directions for understanding the fluorescence of PAH derivatives.

Computational investigations of excited state dynamics of benzo[a]pyrene and substituted derivatives in gas phase and solution

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ACS Fall 2022

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