The two electron electro-oxidation of N,N-dimethylphenylene-1,4-diamine and
related compounds in aqueous solution leads to the formation of the corres
ponding 1,4-diimine which reacts with a range of thiol compounds. The resul
ting ring substituted (R-S-) diamine is further oxidised leading to an incr
ease in the oxidative current which is proportional to the concentration of
the thiol species. The electrode responses were found to be selective towa
rds species including cysteine and homocysteine containing sulfhydryl group
s (RSH) with no reaction observed with either methionine (CH3SCH2CH(COOH)NH
2) or cystine (cystein-S-S-cysteine). The potential required to oxidise the
ring substituted diamine is found to be dependent upon the nature of the t
hiol constituent and may allow some scope for speciation studies.