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Reiter, Sebastian; Keefer, Daniel; Vivie-Riedle, Regina de (2018): RNA Environment Is Responsible for Decreased Photostability of Uracil. In: Journal of the American Chemical Society, Vol. 140, No. 28: pp. 8714-8720
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UV light can induce chemical reactions in nucleic acids and thereby damage the genetic code. Like all of the five primary nucleobases, the isolated RNA base uracil exhibits ultrafast, nonradiative relaxation after photoexcitation, which helps to avoid photodamage most of the time. Nevertheless, within RNA and DNA strands, commonly occurring photolesions have been reported and are often ascribed to long-lived and delocalized excited states. Our quantum dynamical study now shows that excited-state longevity can also occur on a single nucleobase, without the need for delocalization. We include the effects of an atomistic RNA surrounding in wave packet simulations and explore the photorelaxation of uracil in its native biological environment. This reveals that steric hindrance through embedding in an RNA strand can inhibit the ultrafast relaxation mechanism of uracil, promoting excited-state longevity and potential photodamage. This process is nearly independent from the specific combination of neighboring bases.