Studies of phenazine methosulphate (PMS)-catalyzed O2 exchange and phosphorylation in spinach chloroplasts reveal that at short wavelengths (<680 mμ) PMS acts at a reduced quantum efficiency as an oxidant for O2 evolution with concomitant phosphorylation. The quantum yield profile of phosphorylation obtained with PMS differs markedly from the yield profile of phosphorylation for normal chloroplasts with NADP+ or ferricyanide as oxidant. Between 525 and 680 mμ the quantum yield of phosphorylation (ATP) catalyzed by PMS is less than half the constant maximum ATP of the normal system. The maximum ATP value for the normal system is approx. 0.16 ATP/hv. With the PMS system a peak in the yield at 690 mμ is obtained approaching the ATP value of the normal system. This yield falls again at longer wavelengths (>700 mμ). The addition of ascorbate to the PMS phosphorylating system decreases the short-wavelength (<680 mμ) phosophorylation activity but increases the long-wavelength (>690 mμ) phosphorylation activity. The quantum yield profile of this system, showing a long-wavelength rise in phosphorylation efficiency is obtained with or without the addition of 3(3,4-dichlorophenyl)-1, 1-dimethylurea. These experiments have been interpreted as indicating two separate electrontransfer processes catalyzed by PMS, one in which PMS acts at a reduced efficiency as a Hill oxidant, and the other in which PMS acts as an electron donor and acceptor in a cyclic fashion in sensitizing and essentially long-wavelength phosphorylation process. |