Role of membrane charge and semiquinone structure on naphthosemiquinone derivatives and 1,4-benzosemiquinone disproportionation and membrane-buffer distribution coefficients

Semiquinone membrane/buffer partition coefficients have been determined for 1,2-naphthosemiquinone (ONQ(.-)), 1,4-naphthosemiquinone (NQ(.-)) and two of its hydroxylated derivatives, 5,8-dihydroxy1,4-naphthosemiquinone (NZQ(.-)) and 5-hydroxy1,4-naphthosemiquinone (JQ(.-)) as a function of membrane charge in multilamellar vesicles of phosphatidylcholine (PC) and equimolar mixtures of this lipid and phosphatidic acid (PC:PA) and cetyltrimethylammonium bromide (PC:CTAB) at physiological pH with the exception of values corresponding to PC:PA mixtures which were obtained at pH 9. These coefficients follow the order PC:PA<PC<PC:CTAB in agreement with the negative charge of the semiquinones. The disproportionation equilibria of the naphthosemiquinone derivatives are shifted to the semiquinone in the presence of neutral and positive membranes, being more pronounced in the latter. However, very low partition coefficients as well as small shifts in the semiquinone disproportionation equilibrium were observed for ONQ(.-) as compared to the other semiquinones. No partition of 1,4-benzosemiquinone (BQ(.-)) into the lipid phase was detected for either charged or neutral lipid membranes. The presence of lipid membranes decreases the BQ(.-) equilibrium concentration in the presence of all the types of membranes considered here.