Lucigenin: Redox Potential in Aqueous Media and Redox Cycling with O−2 Production1

The use of lucigenin luminescence as a measure of [O−2] has been questioned because lucigenin has been shown to be capable of mediating the production of O−2. This being the case, lucigenin can signal the presence of O−2 even in systems not producing it in the absence of lucigenin. The reduction potential of lucigenin should be in accord with its ability to mediate O−2 production; but it has not heretofore been measured in aqueous media. The problems facing such measurement are the insolubility of the divalently reduced form, which deposits on the electrode, and the slow conformational transition that follows the second electron transfer and which interferes with reversibility. We have now used rapid scan cyclic voltammetry to determine that the reduction potential for lucigenin is −0.14 ± 0.02 V versus the normal hydrogen electrode. This value applies to both the first and the second electron transfers to lucigenin and it is in accord with the facile mediation of O−2 production by this compound.