Direct spectroscopy of contact charge transfer states: Possible consequences for tryptophan excited-state deactivation pathways by O2 and formation of reactive oxygen species
文献情報
Swen Siegert, Ferdinand Vogeler, Joachim Schiedt, Rainer Weinkauf
This paper demonstrates that photodetachment photoelectron spectroscopy (PD-PES) of non-covalently bound heteromolecular anion clusters allows direct access to neutral contact charge transfer (CCT) states. The 2,2′-bithiophene·indole cluster is investigated as a model system in such a way that both chromophores have similar optical excitation cross-sections and hence the PD-PES shows the signature of both molecules. For the complexes O2·stilbene, O2·indole and O2·N-methylindole the optical cross-sections of the conjugated chromophores are much larger than that of O2. This forces most of the anion-to-neutral photoexcitation into the CCT state. The CCT states lie below S1 for 2,2′-bithiophene·indole and O2·stilbene or even below T1 for O2·indole and O2·N-methylindole. Significant differences are found between the PD-PES of O2 with indole and N-methylindole indicating that different collision sites may have different CCT state energies and as a result different 1Δg oxygen formation efficiencies. We discuss the possible consequences of the energetics and the geometry changes for the excited-state deactivation of tryptophan via the CCT state O2−·tryptophan+.
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Biocatalysis and Biotransformation

NDT & E International

Bioorganic & Medicinal Chemistry Letters

Topics in Catalysis

Colloid Journal

Journal of the Indian Institute of Science

Herald of the Russian Academy of Sciences

Heteroatom Chemistry

Journal of Asian Natural Products Research

Journal of Chemical Sciences
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