The inorganic biochemistry of photosynthetic oxygen evolution/water oxidation.
At the request of the organizer of this special edition, we have attempted to do several things in this manuscript: (1) we present a mini-review of recent, selected, works on the light-induced inorganic biogenesis (photoactivation), composition and structure of the inorganic core responsible for photosynthetic water oxidation; (2) we summarize a new proposal for the evolutionary origin of the water oxidation catalyst which postulates a key role for bicarbonate in formation of the inorganic core; (3) we summarize published studies and present new results on what has been learned from studies of 'inorganic mutants' in which the endogenous cofactors (Mn(n+), Ca2+, Cl-) are substituted; (4) the first DeltapH changes measured during the photoactivation process are reported and used to develop a model for the stepwise photo-assembly process; (5) a comparative analysis is given of data in the literature on the kinetics of substrate water exchange and peroxide binding/dismutation which support a mechanistic model for water oxidation in general; (6) we discuss alternative interpretations of data in the literature with a view to forecast new avenues where progress is needed.
Ananyev
G M
GM
Princeton University Department of Chemistry, Hoyt Laboratory, Princeton, NJ 09544, USA.
Zaltsman
L
L
Vasko
C
C
Dismukes
G C
GC
D001665:Binding Sites; D002118:Calcium / Q000737:chemistry; D002374:Catalase / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D019143:Evolution, Molecular; D008345:Manganese / Q000737:chemistry; D013058:Mass Spectrometry; D008956:Models, Chemical; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010788:Photosynthesis; D045322:Photosynthetic Reaction Center Complex Proteins / Q000737:chemistry*; D013997:Time Factors; D014867:Water / Q000737:chemistry*
D002712:Chlorides; D045322:Photosynthetic Reaction Center Complex Proteins; D014867:Water; D008345:Manganese; D002374:Catalase; D010100:Oxygen; D002118:Calcium