Generation of the Thymine Triplet State by Through-Bond Energy Transfer

This is the peer reviewed version of the following article: Chem. Eur. J. 2019, 25, 7004 7011, which has been published in final form at https://doi.org/10.1002/chem.201900830. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[EN] Benzophenone (BP) and drugs containing the BP chromophore, such as the non-steroidal anti-inflammatory drug ketoprofen, have been widely reported as DNA photo-sensitizers through triplet-triplet energy transfer (TTET). In the present work, a direct spectroscopic fingerprint for the formation of the thymine triplet ((3)Thy*) by through-bond (TB) TTET from (BP)-B-3* has been uncovered. This has been achieved in two new systems that have been designed and synthesized with one BP and one thymine (Thy) covalently linked to the two ends of the rigid skeleton of the natural bile acids cholic and lithocholic acid. The results shown here prove that it is possible to achieve triplet energy transfer to a Thy unit even when the photosensitizer is at a long (non-bonding) distance.Financial support from the Spanish Government (Grant SEV-2016-0683 and Projects CTQ2012-38754-C03-03 and CTQ2015-70164P), the Generalitat Valenciana (Prometeo Program), and the Universitat Politecnica de Valencia (pre-doctoral FPI fellowship for P.M.) is gratefully acknowledged.Miró, P.; Gomez-Mendoza, M.; Sastre Navarro, GI.; Cuquerella Alabort, MC.; Miranda Alonso, MÁ.; Marín García, ML. (2019). Generation of the Thymine Triplet State by Through-Bond Energy Transfer. Chemistry - A European Journal. 25(28):7004-7011. https://doi.org/10.1002/chem.201900830S700470112528Mouret, S., Baudouin, C., Charveron, M., Favier, A., Cadet, J., & Douki, T. (2006). Cyclobutane pyrimidine dimers are predominant DNA lesions in whole human skin exposed to UVA radiation. 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