PHOTOCHEMICAL REDUCTION AND OXIDATION OF MENADIONE (VITAMIN K3) IN CHLOROPLASTS

1. Menadione (vitamin K³) was found to be completely reduced byilluminated spinach chloroplasts under highly anaerobic conditionand in the presence of ethylenediamine tetraacetate (EDTA) inthe reaction mixture. This photoreductive reaction is sensitivetoward heat-treatment and inhibited by 2?10^-3M hydroxylamine.
2. In the presence of oxygen, the reduced form of menadione israpidly photooxidized by chloroplasts. This photooxidative activityalso is suppressed by heat-treatment but not inhibited by hydroxylamine.
3. Dyes which are inefficient as HILL oxidants such as thionineand methylene blue were found to be readily reduced by illuminatedchloroplasts, if the experimental conditions were appropriateto prevent the reoxidation of the photoreduced dyes; i.e., exhaustiveremoval of oxygen and the addition of EDTA in the reaction mixture.Menadione was found to accelerate the HILL reaction with thesedyes as oxidant under such experimental conditions.
4. In thepresence of molecular oxygen in the reaction mixture,menadionewas found to inhibit the HILL reaction with 2,6–dichlorophenolindophenol as oxidant, while the reaction rate was little influencedin high anaerobiosis.
5. These findings are explained by theintermediary oxidation and(photo-) reduction of menadione asan intermediary hydrogencarrier, and by the trends toward rapidphotooxidation of reducedmenadione.

(Received July 2, 1960; )