Nanoscale photosynthesis: photocatalytic production of hydrogen by platinized photosystem I reaction centers.

A study of the photocatalytic production of molecular hydrogen from platinized photosystem I (PSI) reaction centers is reported. At pH 7 and room temperature metallic platinum was photoprecipitated at the reducing end of PSI according to the reaction, [PtCl6]2- + 4e- + hv-->Pt decreases + 6Cl-, where it interacted with photogenerated PSI electrons and catalyzed the evolution of molecular hydrogen. The reaction mixture included purified spinach PSI reaction centers, sodium ascorbate and spinach plastocyanin. Experimental data on real-time catalytic platinum formation as measured by the onset and rates of hydrogen photoevolution as a function of time are presented. The key objective of the experiments was demonstration of functional nanoscale surface metalization at the reducing end of isolated PSI by substituting negatively charged [PtCl6]2- for negatively charged ferredoxin, the naturally occurring water-soluble electron carrier in photosynthesis. The data are interpreted in terms of electrostatic interactions between [PtCl6]2- and the positively charged surface of psaD, the ferredoxin docking site situated at the stromal interface of the photosynthetic membrane and which is presumably retained in our PSI preparation. A discussion of the rates of hydrogen evolution in terms of the structural components of the various PSI preparations as well as of those of the intact thylakoid membranes is presented.