Femtosecond transient IR absorption spectroscopy was used to probe the decay mechanism of electronically excited thymine (a naturally occurring pyrimidine base in DNA) dissolved in an ionic liquid ([Bmim][BF 4 ]) or CD 3 CN after the absorption of UV light (267 nm). In both solvents, an absorption band grew on a picosecond timescale, along with decaying bleach and evolving red-shifted absorption signals. A population analysis of the observed kinetic data suggested that most of the photoexcited thymine underwent a sub-picosecond non-radiative relaxation to the vibrationally hot ground electronic state. About 4% (16%) of the excited thymine in the ionic liquid (CD 3 CN) relaxed to an intermediate electronic state, which relaxed into a low-lying triplet state by intersystem crossing (ISC) (ISC did not relax to the ground electronic state within the experimental period (1 ns)). The low ISC yield for thymine in an ionic liquid was correlated with molecular properties of the solvent. This observation is significant because the ISC to triplet state transition for excited thymine has been considered as a precursor to cyclobutane-pyrimidine dimer formation, which led to functional damage of the base after UV absorption. This finding may shed light on the photostability of DNA in ionic liquids.
Keywords: Femtosecond infrared spectroscopy, Thermal relaxation, Cyclobutane-pyrimidine dimer,Ionic liquid, Photostability of thymine DNA is a prime biological molecule because it contains genetic instructions for the growth and function of the cells that constitute all living organisms. 1,2 Alterations to the genetic integrity affect normal life processes. 2 In addition to its biological significance, DNA is increasingly used as a powerful nanotechnology tool due to its conformational polymorphism (e.g., as a hybrid catalyst in the synthesis of highly enantioselective and asymmetric molecules). 3-6 DNA structure and stability preservation is hindered by a lack of appropriate media. 7,8 Aqueous solutions are considered an important DNA preserver for short-and long-term applications 8,9 ; however, the low solubility of organic reactants in water hinders further efficient use of aqueous solutions.In this context, ionic liquids (ILs) have been established as a unique non-aqueous solvent to preserve DNA for longterm use at ambient temperatures. 10,11 ILs contain an organic cation and an inorganic or organic anion with minimal symmetry; they remain liquid below 373 K. 12-15 ILs possess unique green solvent characteristics, such as a negligible vapor pressure, low flammability, wide solubility range, chemical inertness, and wide electrochemical window. 13,16,17 Electrostatic interactions among the IL cation and DNA (i.e., hydrophobic interactions between the hydrocarbon chains of the IL and the bases of DNA) and intermolecular hydrogen bonding between the anion of the IL and the bases of DNA have been established as the main causes for the high stability of DNA in ILs. 11,18-21 So far, examinations of the interactions between DNA and ILs ...