Type I and Type Ii Mechanisms in the Photooxidation of L‐tryptophan and Tryptamine Sensitized by Hematoporphyrin in the Presence and Absence of Sodium Dodecyl Sulphate Micelles

Oxygenated aqueous solutions (pH 10) of L‐tryptophan or tryptamine containing hematopor‐phyrin and/or specific quenchers of the possible reactive intermediates were irradiated with visible light in the presence and in the absence of dispersions of sodium dodecyl sulphate micelles. The rate of loss of the indole derivatives was followed over several min. In the absence of dispersed micelles, indole derivatives appeared to be photooxidized largely by a type I mechanism involving electron transfer from triplet hematoporphyrin to the indole moiety. A type II ( l O 2 ‐involving) mechanism was of minor importance. The presence of sodium dodecyl sulphate micelles, where the porphyrin was solubilized in a monomeric state, exerted only a slight influence on the competition between the two reaction pathways described above in the case of tryptophan, which was essentially all present in the aqueous phase. On the other hand, tryptamine, when dissolved within micelles, underwent photooxidative attack exclusively by 1 O 2 which was generated within a micelle, diffused through the aqueous phase and penetrated into another (tryptamine‐containing) micelle; the reduced efficiency of the latter photoprocess was probably a consequence of the low probability of 1 O 2 penetration into charged micelles.