
Journal of the American Chemical Society p. 1245 - 1251 (1986)
Update date:2022-07-29
Topics:
Freedman, Kenn A.
Becker, Ralph S.
Laser-flash and steady-state excitation accompanied by high-pressure liquid chromatography (HPLC) have been used to evaluate the quantum yields of isomerization (Φ) of the 9-cis-, 11-cis-, 13-cis, and all-trans-n-butylamine Schiff bases of retinals, as well as their protonated analogues.In hexane, for all the Schiff bases, the Φ were = 0.01 and a ground-state transient species was formed after excitation and was seen to decay to the original isomer with lifetimes dependent on solvent polarity.In methanol, all Schiff bases, except the 13-cis isomer, showed relatively high values of Φ.For the latter solvent and for the 9-cis and 11-cis isomers, the all trans-isomer was formed but the 13-cis isomer showed more complicated behaviour, while for the all-trans isomer a mixture of cis isomers was produced.No triplet transients were observed.In the case of the protonated Schiff bases, 11-cis isomerized to the all-trans with high quantum yields in both solvents and no transients were seen.For the protonated all-trans, a mixture of cis isomers was produced where the relative proportions of each was solvent dependent and no transients were seen.For both protonated 9-cis and 13-cis isomers in both solvents, difference spectra did not correspond to the formation of the "normal" all-trans isomer, but analysis by HPLC showed retention times corresponding to "normal" all-trans.Explanations are offered of the results for the latter protonated cases, as well as for the unproptonated 13-cis Schiff base in methanol.The overall results are considered pertinent to the primary reactions in the visual process (rhodopsin and isorhodopsin) and halobacterium halobium (light-adapted and dark-adapted bacteriorhodopsin) from which meaningful comparisons and new insights arise.
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