Reaction mechanisms responsible for transformation of pertechnetate in photoautotrophic organisms

Experimental data on the physiological effects of Tc on photoautotrophic and N2-fixing organisms all suggest a relation between their ability to generate strong reducing power and the incorporation of Tc. A series of biochemical experiments were undertaken to elucidate this problem. Isolated spinach chloroplasts, thylakoids and purified compounds of the photosynthetic electron transport chain were incubated with TcO4-. After illumination, the quantity of TcO4- transformed was measured with gel filtration chromatography. For part of the samples, the amount of extractable Tc(V) was determined. Isolated thylakoids showed reduction of TcO4- in the light, suggesting direct interference of TcO4- with the electron transport chain. Use of specific inhibitors and artificial electron carriers indicated that TcO4- withdraws electrons from ferredoxin. Competitive inhibition of TcO4- reduction by O2 and NADP+, as well as its capacity to function as a terminal acceptor in the diaphorase reaction with NADPH, indicates its interaction with the transport chain to be comparable to that of O2. In suspensions of thylakoids, TcO4- is mainly reduced into an extractable Tc(V) compound. Only part of the Tc fraction reduced by intact chloroplasts could, however, be extracted, whereas negligible quantities of unstable Tc(V) complexes were detected in intact plants. The stable complexes in vivo are supposed to originate through ligand exchange with strong complexing agents, such as thiol compounds. Disproportionation reactions of unstable Tc(V) compounds might result in complexes with Tc in lower oxidation states.