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Excited-State Electronic Properties of 6-Methylisoxanthopterin (6-MI): An Experimental and Theoretical Study

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journal contribution
posted on 08.03.2012 by Goutham Kodali, Madhavan Narayanan, Robert J. Stanley
6-Methylisoxanthopterin (6-MI) is a pteridine-based guanine analog that has a red-shifted absorption and high fluorescence quantum yield. Its Watson–Crick base-pairing and base stacking properties are similar to guanine. The fluorescence quantum yield of 6-MI is sensitive to its nearest neighbors and base stacking, making it a very useful real-time probe of DNA structure. The fundamental photophysics underlying this fluorescence quenching by base stacking is not well understood. We have explored the excited-state electronic structure of the 6-MI in frozen 77 K LiCl glasses using Stark spectroscopy. These measurements yielded the direction and degree of charge redistribution for the S0→S1 transition as manifested in the difference dipole moment, Δμ⃗01, and difference static polarizability, TrΔα⃗⃗. TDDFT (time-dependent density functional theory) was employed to calculate the transition energy, oscillator strength, and the dipole moments of the ground and lowest optically bright excited state of 6-MI (S0→S1). The direction of Δμ⃗01 was assigned in the molecular frame based on the Stark data and calculations. These results suggest that the C4O and C2-NH2 groups are electron-deficient in the excited state, a very different outcome compared with guanine. This implies that Watson–Crick hydrogen bonding in 6-MI may be modulated by absorption of a photon so as to strengthen base pairing, if only transiently. Solvatochromism was also obtained for the absorption and emission spectra of 6-MI in various solvents and compared with the Stark spectroscopic results using both the Lippert-Mataga and Bakhshiev models.