Singlet molecular oxygen [O₂(¹Δ_g)]-mediated photodegradation of tyrosine derivatives in the presence of cationic and neutral micellar systems

The kinetics of rose bengal-sensitized photooxidation of tyrosine and several tyrosine-derivatives (tyr-D) named tyrosine methyl ester, tyrosine ethyl ester and tyrosine benzyl ester was studied in buffered pH 11 water, and buffered pH 11 micellar aqueous solutions of 0.01 M cetyltrimethylammonium chloride (CTAC) and 0.01 M-octylphenoxypolyethoxyethanol [triton X100 (TX100)]. Through time-resolved phosphorescence detection of singlet molecular oxygen (O-2((1)Delta(g))) and polarographic determination of oxygen consumption, the respective bimolecular rate constants for reactive (k(r)) and overall (k(t)) quenching of the oxidative species by tyr-D were evaluated. Both rate constants behave in different fashion depending on the particular reaction medium. k(r)/k(t) values, increase in the sense CTAC << TX100 < water, indicating, for the tyr-D family studied, an excellent degree of self-protection against O-2((1)Delta(g))-attack in the CTAC micellar system and a high photooxidability level in water. Results were interpreted in terms of a competition between solvent polarity effects, local substrate concentration and electron donating capabilities of the substrates in the different media that can contribute to predict the extent of photodynamic damage in biological environments.