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Nonlinear Effects and a Cascade of Radical Events Leading to Laser‐Specific Generation of Active Oxygen Species

Laser photolysis of benzoyl radical precursors (such as PhCOC[OH]R2) in oxygen‐containing solutions leads to a laser‐specific cascade of oxidative events in which benzoyl peroxyl radicals undergo self‐reaction, ultimately leading to the sequential formation of benzoyloxyl, phenyl and phenyl peroxyl radicals. Thus, photoreactions producing benzoyl (PheO) radicals lead to Ph?O under conditions where benzoyl radicals do not decarbonylate. These reactions require the high‐intensity conditions that can only be achieved under pulsed laser excitation; yet, they do not involve any multiphoton processes. Type I mechanisms of this type may be of importance as new laser‐based therapeutic technologies are developed.