Triplet photoreactivity of the diaryl ketone tiaprofenic acid and its decarboxylated photoproduct. Photobiological implications.
The 2-benzoylthiophene chromophore of the photosensitizing drug tiaprofenic acid and of its decarboxylated derivative is characterized by a unusually high energy gap between the T1 (pi, pi*) and T2 (n, pi*) excited states, which makes this a unique system to study the intrinsic photoreactivity of the two states. Weak fluorescence and phosporescence emission were detected at room temperature. Tiaprofenic acid undergoes photodecarboxylation from the triplet manifold as the main reaction. The photoprocess is temperature dependent with activation energy of 7-10 kcal/mol, close to the energy gap between T1 and T2. The decarboxylated product abstracts hydrogen in type I reactions. The involvement of T2 in the above processes is proposed. Moreover the decarboxylated derivative exhibits reactivity toward phenols, consistent with a participation of the T1 state as electron acceptor. The observed photoprocesses can account for biological photosensitization reactions, like membrane damage and protein modification.
Encinas
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S
Departamento de Química/Instituto de Tecnología Química UPV-CSIC, Universidad Politécnica, Valencia, Spain.
Miranda
M A
MA
Marconi
G
G
Monti
S
S
D003653:Decarboxylation; D019281:Dimerization; D049449:Luminescence; D010782:Photolysis; D017319:Photosensitizing Agents / Q000737:chemistry*; D011422:Propionates / Q000737:chemistry* / Q000528:radiation effects; D013050:Spectrometry, Fluorescence; D013816:Thermodynamics
D017319:Photosensitizing Agents; D011422:Propionates; C021270:tiaprofenic acid