Comprehensive photochemistry and photophysics of land- and marine-based beta-carbolines employing time-resolved emission and flash transient spectroscopy.
The photophysical and photochemical behavior of Norharmane (Norh), Harmane (Hara) and Harmine (Hari) and their cations have been examined as a function of the nature of the solvent. Time-resolved emission in nonprotic polar solvents showed fluorescence for all and also phosphorescence for Hari. All emissions were assigned as those of the neutral molecules. Norh and Hari showed fluorescence of both the neutral and the cation in methanol as well as phosphorescence of the neutral while Hari also had fluorescence of the zwitter ion. In ethanol, Norh and Hari displayed fluorescence and phosphorescence of the neutral. The ground-state cations of Norh and Hari exhibited fluorescences of the cation and Hari also had a phosphorescence (cation). The flash transient spectra in nonprotic solvents of all three carbolines had long-lived triplet transients only of the neutral. Triplet and singlet oxygen yields were quite high, 0.31-0.40. Direct excitation of any of the cations gave only the cation triplet. The triplet yields of the cations appear to be low (0.01-0.10 range). Theoretical calculations were done relative to location of triplet states. Some new information will be reported on other naturally occurring differently substituted marine-based beta-carbolines. The impact of all of the foregoing observations on the photosensitizing potential of all compounds is discussed.
Becker
Ralph S
RS
Centro de Quimica-Fisica Molecular-Complexo Interdisciplinar, Instituto Superior Tecnico, 1049-001 Lisbon, Portugal. ralphbecker25@sbcglobal.net
Ferreira
Luis F V
LF
Elisei
Fausto
F
Machado
Isabel
I
Latterini
L
L
D000818:Animals; D002243:Carbolines / Q000737:chemistry*; D006247:Harmine / Q000031:analogs & derivatives / Q000737:chemistry; D008386:Marine Biology; D015394:Molecular Structure; D010777:Photochemistry; D013057:Spectrum Analysis; D014561:Urochordata / Q000737:chemistry*
D002243:Carbolines; D006247:Harmine; C005010:harman; C010262:norharman