Photosynthesis is one of the fundamental processes of life on Earth. The evolutionary transition from anoxygenic (no oxygen produced) to oxygenic (oxygen-producing) photosynthesis resulted in the critical development of atmospheric oxygen in amounts large enough to allow the evolution of organisms that use oxygen, including plants and mammals.

One of the outstanding questions of the early Earth is how ancient organisms made this transition. A team of scientists from Arizona State University has moved us closer to understanding how this occurred, in a paper recently published in the Proceedings of the National Academy of Sciences. The paper is authored by James Allen, JoAnn Williams, Tien Le Olson, Aaron Tufts, Paul Oyala and Wei-Jen Lee, all from the Department of Chemistry and Biochemistry in ASU's College of Liberal Arts and Sciences.

Plants and algae, as well as cyanobacteria, use photosynthesis to produce oxygen and "fuels," the latter being oxidizable substances like carbohydrates and hydrogen. There are two pigment-protein complexes that orchestrate the primary reactions of light in oxygenic photosynthesis: photosystem I and photosystem II.

"In photosynthesis, the oxygen is produced at a special metal site containing four manganese and one calcium atom connected together as a metal cluster," explains professor James Allen. "This cluster is bound to the protein called photosystem II that provides a carefully controlled environment for the cluster."

On illumination, two water molecules bound at the cluster are split into molecular oxygen and four protons. Since water molecules are very stable, this process requires that the metal cluster be capable of efficiently performing very energetic reactions.

Allen, Williams and coworkers are trying to understand how a primitive anoxygenic organism that was capable of performing only simple low energy reactions could have evolved into oxygen-producing photosynthesis.

They have been manipulating the reaction center of the purple bacterium Rhodobacter sphaeroides encouraging it to acquire the functions of photosystem II. In the recent publication, they describe how a mononuclear manganese bound to the reaction center has gained some of the functional features of the metal cluster of photosystem II.

Although the mononuclear manganese cannot split water, it can react with reactive oxygen species to produce molecular oxygen. These results suggest that the evolution of photosynthesis might well have proceeded through intermediates that were capable of oxygen production and served until a protein with a bound manganese-calcium cluster evolved.