LASER PHOTOLYSIS OF RETINAL AND ITS PROTONATED AND UNPROTONATED n-BUTYLAMINE SCHIFF BASE |
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Authors: | Michael M. Fisher Karl Weiss |
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Affiliation: | Photochemistry and Spectroscopy Laboratory, Department of Chemistry, Northeastern University, Boston, Massachusetts, 02115, U.S.A. |
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Abstract: | Abstract —The pulsed ruby laser (347 nm) flash photolysis technique has been used to measure the triplet-triplet absorption spectra and triplet lifetimes of trans -retinal, N-frans -retinylidene- n -butylamine (NRBA), and protonated NRBA (NRBAH+) at room temperature. In methylcyclohexane solution, the triplet lifetimes are in the range 10–20 μs and decrease in the order NRBAH+ > NRBA > trans -retinal. Intersy stem-crossing efficiencies (φISC) were determined by a comparison technique using anthracene and 1,2-benzanthracene as reference compounds. For trans -retinal, φISC is 0–50 pM 0–05 in methylcyclohexane and 0–08 in methanol, which confirms that earlier values of 0–11 and 0–017 in these solvents are in error. For NRBA and NRBAH+ in methylcyclohexane, ΦISC values are 0008 and < 0–001, respectively. Evidence is presented for a significant solvent effect in the isomerization of retinal via the triplet state, and that cis φ trans isomerization occurs from the triplet state of NRBAH+. The relation between the intersystem-crossing properties of model compounds and the photochemistry of rhodopsin is discussed. |
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