A universal way to establish near-electrode effects is to compare the results of electrolysis with the results of the cor r esp ondi ng ho mog en eou s reaction. In this regard, we began in 1973 to apply processes with homogeneous catalytic endergonic ET (CENET) -with "exter nal" intermolecular activation , first review , by analogy with "int er nal" molecular activation by introducing an electronegative substituent . In this way we obtained in quantitative yield alanine from "protected" p-nitrocarbobenzoxyalanine using the anion radical of 4-nitrodiphenyl, a more easily electroreduced "external" activator, homogeneous ETcatalyst, CENET 1973, 1975 p. 141), and preparative electrolysis can be carried out in the potential region beyond the discharge of the background electrolyte . In this way it is possible to carry out kinetic measurements for cases of strongly endoergic ET; among the first examples we took in particular the chlorophyllcarotene system, which has an important role in photosynthesis (ΔE 0 = -0.41V, solvent DMF-benzene) .