Benzo[a]pyrene is a widespread environmental pollutant and a strong carcinogen. It is important to understand its bio-toxicity and degradation mechanism. Herein, we studied the excited state dynamics of benzo[a]pyrene by using time-resolved fluorescence and transient absorption spectroscopic techniques. For the first time, it is identified that benzo[a]pyrene in its singlet excited state could react with oxygen, resulting in fluorescence quenching. Additionally, effective intersystem crossing can occur from its singlet state to the triplet state. Furthermore, the interaction between the excited benzo[a]pyrene and ct-DNA can be observed directly and charge transfer between benzo[a]pyrene and ct-DNA may be the reason. These results lay a foundation for further understanding of the carcinogenic mechanism of benzo[a]pyrene and provide insight into the photo-degradation mechanism of this molecule.

Triplet excited species are clearly identified in both hm⁶A and f⁶A after UV excitation, which is in sharp contrast to the 10⁻³level triplet yield of adenosine scaffolds.

Selenium nucleic acids possess unique properties and have been demonstrated to have a wide range of applications such as in DNA X-ray crystallography and novel medical therapies. However, as a heavy atom, selenium substitution may easily alter the photophysical properties of a nucleic acid by red-shifting the absorption spectra and introducing effective intersystem crossing to triplet excited states. In present work, the excited state dynamics of a naturally occurring selenium substituted uracil (2-selenuracil, 2SeU) is studied by using femtosecond transient absorption spectroscopy as well as quantum chemistry calculations. Ultrafast intersystem crossing to the lowest triplet state (T₁) and effective non-radiative decay of this state to the ground state (S₀) are demonstrated in the neutral form 2SeU. However, the triplet lifetime of the deprotonated form 2SeU is found to be almost one order of magnitude longer than that in the neutral one. Quantum chemistry calculations indicate that the short triplet lifetime in 2SeU is due to excited state population decay through a crossing point between T₁ and S₀. In the deprotonated form, shortening the N1–C2 bond length makes the structural distortion more difficult and brings a larger energy barrier on the pathway to the T₁/S₀ crossing point, resulting in one order of magnitude increase of the triplet state lifetime. Our study reveals one key factor to regulate the triplet lifetime of 2SeU and sets the stage to further investigate the photophysical and photochemical properties of 2SeU-containing DNA/RNA duplexes.