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Issue 3, 2012
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Diffusion-controlled sensitization of photocleavage reactions on surfaces

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Abstract

The kinetic rate equation for the photosensitized cleavage reaction of surface-bound photolabile chromophores with free diffusion of sensitizer molecules from the bulk of a solution to the surface is derived by determining the stationary solution of a diffusion equation with suitable boundary conditions. The relation between the phenomenological rate constant for the photosensitized reaction at the surface and in the bulk is established. Applying the result to the analysis of an experimental example, the origin of the quasi zeroth-order kinetics of the sensitized reaction is revealed. A theoretical comparison of intramolecular sensitization in photocleavable protecting groups with a molecular antenna and sensitization with the freely diffusing sensitizer shows that in a typical case sensitization with free diffusion is more effective than intramolecular sensitization for sensitizer concentrations higher than 5 mM.

Graphical abstract: Diffusion-controlled sensitization of photocleavage reactions on surfaces

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Publication details

The article was received on 28 Sep 2011, accepted on 03 Nov 2011 and first published on 05 Jan 2012


Article type: Paper
DOI: 10.1039/C1PP05319A
Citation: Photochem. Photobiol. Sci., 2012,11, 533-538
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    Diffusion-controlled sensitization of photocleavage reactions on surfaces

    D. Wöll, N. Lukzen and U. E. Steiner, Photochem. Photobiol. Sci., 2012, 11, 533
    DOI: 10.1039/C1PP05319A

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