Transient thiyl radicals in yeast copper(I) thionein

In an EPR study employing yeast copper(I) thionein, GSH and Cu-GSH it was shown that thiyl radicals could be successfully generated from the thiolate sulfur via oxidation by photochemically formed superoxide at 77 K. The g-value was 2.036. Essentially no EPR detectable copper(II) was monitored under the experimental conditions, indicating that the oxidation reduction process is restricted to the thiolate sulfur. The Cu(I)-thiolate chromophores remained fully intact as deduced from chiroptical and luminescence measurements. Thus, copper thionein is supposed to be actively involved in the scavenging of oxygen free radicals by a reversible thiolate oxidation reduction cycle. The coordinated Cu(I) seems to serve as a prominent candidate to stabilize the transiently formed thiyl radical.