Luminol chemiluminescence: chemistry, excitation, emitter.
The mechanism of luminol chemiluminescence is a special case of nucleophilic addition to carbonyl compounds. The breakdown of the key intermediate, an alpha hydroxy hydroperoxide, produces a peracid ortho to an acyl diazene group. After intramolecular addition of the peracid, the energy from nitrogen expulsion is utilized in the formation of an anti-aromatic endoperoxide. Rupture along the O,O bond leaves a substantial part of the ensuing phthalate in its excited state. The emitter is shown to be a mono-protonated phthalate unaccessible by photoexcitation. The dark reaction is a concerted decomposition of the alpha hydroxy hydroperoxidixe to yield ground-state phthalate.
Merényi
G
G
Department of Physical Chemistry, Royal Institute of Technology, Stockholm, Sweden.
Lind
J
J
Eriksen
T E
TE
D055598:Chemical Phenomena; D002621:Chemistry; D004583:Electrons; D006878:Hydroxides; D017665:Hydroxyl Radical; D008163:Luminescent Measurements; D008165:Luminol; D010084:Oxidation-Reduction; D011724:Pyridazines; D013481:Superoxides
D006878:Hydroxides; D011724:Pyridazines; D013481:Superoxides; D017665:Hydroxyl Radical; D008165:Luminol