Document Type thesis Author Name Benco, John S URN etd-0803100-103547 Title Singlet-Singlet and Triplet-Triplet Energy Transfer in Polychromophoric Peptides Degree MS Department Chemistry & Biochemistry Advisors W. Grant McGimpsey, Advisor James P. Dittami, Department Head Keywords peptides energy transfer Date of Presentation/Defense 2000-05-03 Availability unrestricted
The photophysics of several bichromophoric dipeptide model compounds and two trichromophoric 15-residue peptides have been studied by a combination of absorption, fluorescence, phosphorescence and laser flash photolysis. Intramolecular singlet-singlet energy transfer (SSET) occurs efficiently within these systems. Trichromophore 14 undergoes intramolecular SSET from the central chromophore to the termini, kSSET = 5.8 x109 s-1 , with a five fold increase over 13, kSSET = 1.1 x 109 s-1 .
Evaluation of SSET mechanisms via the Förster treatment and molecular modeling indicates that the dipole-induced dipole mechanism is sufficient to account for the observed SSET. However, given the close distances of the chromophores (~10 Å), an electron exchange mechanism can not be ruled out.
Low-temperature phosphorescence in 1:1 methanol/ethanol and room-temperature laser flash photolysis in acetonitrile results indicate that intramolecular triplet-triplet energy transfer (TTET) is efficient in dipeptides 7,9-12 and proceeds with a rate constant of kTTET > 5 x 10 8 s-1. The occurrence of TTET in dipeptide 8, (biphenyl-naphthalene), could not be confirmed due to the fact that SSET from biphenyl to the naphthalene moiety was 26 times greater than kISC. Thus nearly all absorbed light was funneled directly the to the singlet manifold of the naphthalene moiety.
TTET in the trichromophores could not be fully evaluated due to their low solubility. However, it is shown from 77°K experiments that kTTET is at least 2.2 x 102 and 2.6 x 102 s-1 for 13 and 14 respectively.
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