PCET in Solution

A comparative experimental study of single ET and PCET reactions in the iron biimidazoline complexes shown in Fig. 16.2 indicated that the rates of ET and PCET 

We have also applied this theory to biologically relevant systems, such as PCET in DNA-acrylamide complexes [61]. Experiments implied that PCET may occur in such complexes [62]. The influence of neighboring DNA base pairs was determined theoretically by studying both solvated thymine-acrylamide and solvated DNA-acrylamide models. The calculations indicated that the final product corresponds to single ET for the solvated thymine-acrylamide complex but to a net PCET reaction for the solvated DNA-acrylamide models. This difference is due to a decrease in solvent accessibility in the presence of DNA, which alters the relative free energies of the ET and PCET product states. Thus, the balance between ET and PCET in the DNA-acrylamide system is highly sensitive to the solvation properties of the system. 

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