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Light-induced tryptophan radical generation in a click modular assembly of a sensitiser-tryptophan residue

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Abstract

Click chemistry was used as an efficient method to covalently attach a chromophore to an amino acid. Such easily prepared model systems allow for time-resolved studies of one-electron oxidation reactions by the excitation of the chromophore by a laser flash. The model complex ruthenium—tryptophan (Ru—Trp) has been synthesised and studied for its photophysical and electrochemical properties. Despite a small driving force of less than 100 meV, excitation with a laser flash results in fast internal electron transfer leading to the formation of the protonated radical (Trp·H+). At neutral pH electron transfer is followed by deprotonation to form the neutral Trp· radical with the rate depending on the concentration of water acting as the proton acceptor. The formation of the tryptophan radical was confirmed by EPR.

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Authors and Affiliations

  1. CEA, iBiTec-S, UMR 8221, Service de Bioénergétique Biologie Structurale et Mécanismes (SB2SM), F-91191, Gif-sur-Yvette, France

    Sujitraj Sheth, Aurélie Baron, Christian Herrero, Ally Aukauloo & Winfried Leibl

  2. Centre de Recherche de Gif, Institut de Chimie des Substances Naturelles du CNRS, UPR-2301, 1 Avenue de la Terrasse, F-91198, Gif-sur-Yvette, France

    Aurélie Baron & Boris Vauzeilles

  3. Institut de Chimie Moléculaire et des Matériaux d’Orsay, UMR-CNRS 8182, Université de Paris-Sud XI, F-91405, Orsay, France

    Christian Herrero, Boris Vauzeilles & Ally Aukauloo

Authors
  1. Sujitraj Sheth
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  2. Aurélie Baron
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  3. Christian Herrero
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  4. Boris Vauzeilles
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  5. Ally Aukauloo
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  6. Winfried Leibl
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Corresponding authors

Correspondence to Ally Aukauloo or Winfried Leibl.

Additional information

Electronic supplementary information (ESI) available: Details concerning synthesis, experimental procedures and additional figures mentioned in the text. See DOI: 10.1039/c3pp50021g

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Sheth, S., Baron, A., Herrero, C. et al. Light-induced tryptophan radical generation in a click modular assembly of a sensitiser-tryptophan residue. Photochem Photobiol Sci 12, 1074–1078 (2013). https://doi.org/10.1039/c3pp50021g

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  • DOI: https://doi.org/10.1039/c3pp50021g

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