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Generation and Characterization of Psoralen Radical Cations
Author(s) -
Wood Paul D.,
Johnston Linda J.
Publication year - 1997
Publication title -
photochemistry and photobiology
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.818
H-Index - 131
eISSN - 1751-1097
pISSN - 0031-8655
DOI - 10.1111/j.1751-1097.1997.tb03201.x
Subject(s) - psoralen , chemistry , photochemistry , radical ion , electron transfer , aqueous solution , acetonitrile , reactivity (psychology) , quantum yield , guanosine , hydroxyl radical , radical , organic chemistry , dna , ion , fluorescence , medicine , biochemistry , physics , alternative medicine , pathology , quantum mechanics
— Radical cations of psoralen, 8‐methoxypsoralen(8‐MOP) and 5‐methoxypsoralen have been generated by photosensitized electron transfer in acetonitrile and aqueous buffer/acetonitrile (1:1) and have absorption maxima at 600, 650 and 550 nm, respectively. The radical cations have lifetimes of 5 p.s under these conditions, are unreactive toward oxygen and show behavior typical of ar‐ylalkene radical cations in their reactivity toward nucle‐ophiles and the precursor psoralens. Direct 355 nm excitation of 8‐MOP in aqueous buffer at physiological pH results in monophotonic photoionization to give 8‐MOP * + with a quantum yield of 0.015.The 8‐MOP * + reacts with both guanosine and adenosine mononucleotides ( k = 2.5 times 10 9 and 3.4 times 10 7 M ‐1 s 1 , respectively) via electron transfer to give the purine radical cations, but does not react with pyrimidine mononucleotides. These results suggest that reactions of psoralen radical cations generated by electron transfer or photoionization may be involved in psoralen/UVA therapy.