Thiol peroxyl radical formation from the reaction of cysteine thiyl radical with molecular oxygen: an ESR investigation.

Using Electron Spin Resonance (ESR) spectroscopy, we have identified the cysteine thiol peroxyl radical (CysSOO.) at low temperatures in two aqueous glasses. This radical shows a typical peroxyl radical ESR spectrum, but unlike carbon-based peroxyl radicals has a violet color (lambda max = 540 nm) and forms a new radical showing a singlet ESR spectrum when photobleached with visible light. The cysteine peroxyl radical reacts to form the cysteine sulfinyl radical (CysSO.) in the glass which allows warming to 165K. 17O isotopic substitution studies indicate dissolved molecular oxygen is the source of oxygen in CysSOO.. Anisotropic g-values and the parallel anisotropic 17O hyperfine couplings for this radical are reported.