Photoprotection of 1,4-dihydropyridine derivatives by dyes.

The possibility of increasing the photochemical stability of nisoldipine by using indigotine and azorubine as photoprotectors has been studied. The course of the photodegradation was monitored by means of UV-vis spectrophotometry and HPLC. Quantitative assessments of the nisoldipine photodegradation included evaluation of the quantum yields and kinetic parameters. In order to establish the light intensity absorbed by a system, Reinecke salt was used as a chemical actinometer. The values of the quantum yields (phi) of photodegradation decreased with increasing dye concentration and were 0.24-0.15 and 0.27-0.25 for indigotine and azorubine, respectively. Furthermore, our attention was focused on determination the role of the selected dyes during the photodegradation of nisoldipine and the calculations were made to eliminate an inner filter effect. The values obtained were used to construct a Stern-Volmer plot and calculate the Stern-Volmer constants (KSV). On the basis of the KSV and the values of the quenching constant (kq) the exited state lifetime (tauo) of nisoldipine in the presence of indigotine and azorubine were estimated. The calculated values of tauo for NS were 6.66x10(-6)s--in the presence of indigotine and 2.76x10(-6)s--in the presence of azorubine, indicating that the photodegradation of nisoldipine occurs from the lowest triplet excited state.

Hydrogen-bonded complexes of lumichrome.

Hydrogen bonds were shown to play an important role in the lumichrome photophysics and photochemistry both in solutions and in the solid state. In solutions, lumichrome can form hydrogen-bonded complexes with a variety of molecules, such as acetic acid or methanol, as supported by spectral and equilibrium studies. Photoexcitation of some hydrogen-bonded complexes, having appropriate configuration, as in the case of acetic acid, may lead to excited-state proton transfer, resulting in formation of the isoalloxazinic structure, detectable by its characteristic emission, distinct from that of the intrinsically alloxazinic lumichrome. Theoretical calculations confirmed the role of the hydrogen-bonded complexes, yielding several stable eight-membered cyclic structures of such complexes characterized by spectral changes similar to those observed experimentally. Hydrogen bonds play an essential role in the formation of the lumichrome crystal structure, as follows from the X-ray diffraction results. Interestingly, the crystals studied included molecules of methanol used as solvent in crystal growth. The emission studies of polycrystalline samples, similar to the processes occurring in solutions, point to the importance of hydrogen-bonding interactions in crystal packing allowed by the symmetry of the hydrogen-bonded dimers.