Kinetic analysis of nitroxide radical formation under oxygenated photolysis: toward quantitative singlet oxygen topology
Zigler, D.F.; Ding, E.C.; Jarocha, L.E.; Khatmullin, R.R.; DiPasquale, V.M.; Sykes, R.B.; Tarasov, V.F.; Forbes, M.D. Kinetic analysis of nitroxide radical formation under oxygenated photolysis: toward quantitative singlet oxygen topology. Photochem. Photobiol. Sci. 2014, 13, 12, 1804-1811.
Reaction kinetics for two sterically hindered secondary amines with singlet oxygen have been studied in detail. A water soluble porphyrin sensitizer, 5,10,15,20-tetrakis-(4-sulfunatophenyl)-21,23H-porphyrin (TPPS), was irradiated in oxygenated aqueous solutions containing either 2,2,6,6-tetramethylpiperidin-4-one (TMPD) or 4-[-trimethyl-ammonium]-2,2,6,6-tetramethylpiperidinyl chloride (N-TMPCl). The resulting sensitization reaction produced singlet oxygen in high yield, ultimately leading to the formation of the corresponding nitroxide free radicals (R2NO) which were detected using steady-state electron paramagnetic resonance (EPR) spectroscopy. Careful actinometry and EPR calibration curves, coupled with a detailed kinetic analysis, led to a simple and compact expression relating the nitroxide quantum yield ΦR2NO (from the doubly-integrated EPR signal intensity) to the initial amine concentration [R2NH]i. With all other parameters held constant, a plot of ΦR2NO vs. [R2NH]i gave a straight line with a slope proportional to the rate constant for nitroxide formation, kR2NO. This establishment of a rigorous quantitative relationship between the EPR signal and the rate constant provides a mechanism for quantifying singlet oxygen production as a function of its topology in heterogeneous media. Implications for in vivo assessment of singlet oxygen topology are briefly discussed.
Photochemical & Photobiological Sciences