A viewpoint: Why chlorophyll a?

Chlorophyll a (Chl a) serves a dual role in oxygenic photosynthesis: in light harvesting as well as in converting energy of absorbed photons to chemical energy. No other Chl is as omnipresent in oxygenic photosynthesis as is Chl a, and this is particularly true if we include Chl a (2), (=[8-vinyl]-Chl a), which occurs in Prochlorococcus, as a type of Chl a. One exception to this near universal pattern is Chl d, which is found in some cyanobacteria that live in filtered light that is enriched in wavelengths > 700 nm. They trap the long wavelength electronic excitation, and convert it into chemical energy. In this Viewpoint, we have traced the possible reasons for the near ubiquity of Chl a for its use in the primary photochemistry of Photosystem II (PS II) that leads to water oxidation and of Photosystem I (PS I) that leads to ferredoxin reduction. Chl a appears to be unique and irreplaceable, particularly if global scale oxygenic photosynthesis is considered. Its uniqueness is determined by its physicochemical properties, but there is more. Other contributing factors include specially tailored protein environments, and functional compatibility with neighboring electron transporting cofactors. Thus, the same molecule, Chl a in vivo, is capable of generating a radical cation at +1 V or higher (in PS II), a radical anion at -1 V or lower (in PS I), or of being completely redox silent (in antenna holochromes).