Covalently linked peptide-porphyrin compounds are most suitable systems for fundamental studies aiming to the comprehension of the mechanisms driving photoinduced energy/electron transfer processes. Mimicking photo- synthetic units, the porphyrin groups act as antenna moieties while the peptide chain is the active medium through which energy and/or electron funneling occur. In this contribution we studied the transfer of excitation between two identical tetraphenylporphyrin groups connected by short peptide chains of different length formed by non-coded conformationally constrained α-amino acids, i.e., Cα-methylvaline. The photophysical events following porphyrin photoexcitation were characterized from the microsecond to the picosecond time region by time-resolved spectroscopy techniques. Ultrafast transient absorption measurements revealed the presence of a transient species that we assign to a self-trapped exciton migrating through the peptide chain. The exciton species propagates the electronic coupling between the two porphyrin groups giving rise to a characteristic bisignate band measured by circular dichroism experiments. Molecular dynamics simulations strongly suggest that the long lifetime (hundreds of picoseconds) of the exciton species is determined by the rigidity of the Cα-methyl- valine residues, that inhibited energy relaxation pathways coupled to torsional motions of the peptide chain.

Cimino, R., Gatto, E., De Zotti, M., Formaggio, F., Toniolo, C., Giannetti, M., et al. (2023). Peptide-bridged bis-porphyrin compounds: a photophysical and molecular dynamics study. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY, 16 [10.1016/j.jpap.2023.100191].

Peptide-bridged bis-porphyrin compounds: a photophysical and molecular dynamics study

Gatto E.;Palleschi A.
Software
;
Venanzi M.
Writing – Original Draft Preparation
2023-01-01

Abstract

Covalently linked peptide-porphyrin compounds are most suitable systems for fundamental studies aiming to the comprehension of the mechanisms driving photoinduced energy/electron transfer processes. Mimicking photo- synthetic units, the porphyrin groups act as antenna moieties while the peptide chain is the active medium through which energy and/or electron funneling occur. In this contribution we studied the transfer of excitation between two identical tetraphenylporphyrin groups connected by short peptide chains of different length formed by non-coded conformationally constrained α-amino acids, i.e., Cα-methylvaline. The photophysical events following porphyrin photoexcitation were characterized from the microsecond to the picosecond time region by time-resolved spectroscopy techniques. Ultrafast transient absorption measurements revealed the presence of a transient species that we assign to a self-trapped exciton migrating through the peptide chain. The exciton species propagates the electronic coupling between the two porphyrin groups giving rise to a characteristic bisignate band measured by circular dichroism experiments. Molecular dynamics simulations strongly suggest that the long lifetime (hundreds of picoseconds) of the exciton species is determined by the rigidity of the Cα-methyl- valine residues, that inhibited energy relaxation pathways coupled to torsional motions of the peptide chain.
2023
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/02 - CHIMICA FISICA
English
Bis-porphyrins; Exciton coupling; Peptide spacers; Singlet oxygen production; Time-resolved spectroscopy; Ultrafast transient absorption
Cimino, R., Gatto, E., De Zotti, M., Formaggio, F., Toniolo, C., Giannetti, M., et al. (2023). Peptide-bridged bis-porphyrin compounds: a photophysical and molecular dynamics study. JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY, 16 [10.1016/j.jpap.2023.100191].
Cimino, R; Gatto, E; De Zotti, M; Formaggio, F; Toniolo, C; Giannetti, M; Palleschi, A; Serpa, C; Venanzi, M
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/328644
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