The role of redox-active amino acids in the photosynthetic water-oxidizing complex.

The protein environment can dramatically affect the EPR line shape of tyrosine radicals. The alterations can be caused by: (1) a change in methylene geometry caused by different protein steric constraints; (2) a change in spin density caused by a change in protein environment; or (3) covalent modification of the tyrosine. Any or all of these effects may also be important, in some cases, in control of oxidation potential and chemical reactivity. The new signal that has been observed in the YF161D1 PS II mutant has an approximate 1:3:3:1 lineshape. There is no precedent for a 1:3:3:1 EPR signal from a tyrosine in a powder sample. However, as described above, given the diversity of signals from tyrosine radicals, it is impossible to exclude the possibility that the signal arises from tyrosine on this basis.