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THE STEPWISE BIPHOTONIC PHOTOIONIZATION OF CHLORPROMAZINE AS SEEN BY LASER FLASH PHOTOLYSIS
Author(s) -
BUETTNER GARRY R.,
HALL ROBERT D.,
CHIGNELL COLIN F.,
MOTTEN ANN G.
Publication year - 1989
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1989.tb04103.x
Subject(s) - photoionization , flash photolysis , chemistry , photochemistry , ionization , photodissociation , excited state , laser , atomic physics , kinetics , reaction rate constant , optics , ion , physics , organic chemistry , quantum mechanics
It is generally accepted that both promazine (PZ) and chlorpromazine (CPZ) photoionize monophotonically to their respective cation radicals and the corresponding hydrated electrons. It is also supposed that this photoionization has a role in the phototoxic effects of these drugs. However, using laser flash photolysis, we have observed that photoionization of CPZ during S, excitation (Λ > 300 nm) is a stepwise biphotonic process. In the case of PZ our flash photolysis results are less clear‐cut, but are consistent with stepwise biphotonic photoionization for S, excitation. We demonstrate, using computer simulation of the intramolecular kinetics, that the estimated triplet state lifetime of CPZ is sufficiently long (23 ns at room temperature) to account for the apparent monophotonic photoionization that has been observed by others at high light intensities and short pulse times. Our laser flash photolysis results also suggest that the photo‐ionization mechanism of PZ and CPZ is wavelength‐dependent. Both drugs exhibit apparent monophotonic photoionization when they are excited at 266 nm under conditions of laser pulse width and intensity similar to those at 355 nm. We suggest that photoionization is not an important mechanism in the observed phototoxic and photoal‐lergic effects of PZ and CPZ in sunlight.