Contrasts between oxygenic and anoxygenic photoreduction of ferredoxin: Incompatibilities with prevailing concepts of photosynthetic electron transport

An investigation by paramagnetic resonance spectroscopy of the photoreduction of ferredoxin, oxygenically by water and anoxygenically by a direct electron donor to photosystem I, led to the unexpected findings that different reductive mechanisms may be involved. Ferredoxin photoreduced by water was not reoxidized in the light under aerobic conditions and, under anaerobic conditions, it was remarkably resistant to reoxidation in the dark. By contrast, ferredoxin photoreduced by a donor to photosystem I was readily reoxidized in the light by air and, under anaerobic conditions, by exposure to darkness. Furthermore, when electron transport linking photosystems I and II was inhibited by a plastoquinone antagonist, ferredoxin was photoreduced by water with no evidence for an accompanying photoreduction of the more electronegative bound iron-sulfur centers in chloroplasts. These findings are at variance with the now prevalent concepts of photosynthetic electron transport.