| Abstrakt: |
Factors responsible for fluorescence quenching of the lipophylic fluorescent probe 4-dimethylaminochalcone in nonpolar and polar media were studied. The femtosecond dynamics of 4-dimethylaminochalcone excited state was measured using the absorption method of "excitation probing". In nonpolar hexane where the fluorescence quantum yield is very low (0.001), all excited 4-dimethylaminochalcone molecules go to the triplet state with a rate constant of 2.10(11) s(-1). At the same time, the radiation rate constant is 1000 times lower; therefore, such a fast transition to triplet is the major cause of the very small fluorescence yield. In polar acetone, the fluorescence yield is 220 times higher than in hexane. In acetone, no transitions to triplet state were detected. At the same time, a radiationless conversion to the ground state took place with a rate constant of 10(9) s(-1), which decreased the fluorescence yield to 0.22. The activation energy of the quenching processes is polarity dependent and decreases from 6 in nonpolar to 3 kcal/mol in polar media. The yield of 4-dimethylaminochalcone fluorescence varies hundreds times in media of different polarity but is a linear function of the Lippert's polarity parameter f(epsilon,n) where epsilon is the dielectric constant at low frequencies. It is supposed that polar media stabilize the "flat" conformation of the 4-dimethylaminochalcone molecule prior to its excitation, and this conformation is optimal for fluorescence. In this case, stabilization is determined only by medium polarity. |
