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Although a quenching of dimol CL by DABCO has been observed, it was not possible to perform an adequate quantitative interpretation of the results since dimethyldioxirane was found to be efficiently reactive with DABCO
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Although a quenching of dimol CL by DABCO has been observed, it was not possible to perform an adequate quantitative interpretation of the results since dimethyldioxirane was found to be efficiently reactive with DABCO.
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Notably, photosensitized 1O2 emission quenching experiments with DABCO showed an unusual behaviour in the acidic solvent mixture. Addition of the quencher did not affect the singlet-oxygen lifetime in the low [DABCO] range. Presumably, DABCO becomes protonated and thus is a much less effective quencher as tong as the buffer keeps the pH in the acidic range. Only above [DABCO, 0.127 M a linear increase of τΔ 0/τΔ with [DABCO] was observed yielding k ΔQ, 5.4 × 105 M-1 s-1 as rate constant of 1O2 quenching by DABCO, which compares well with k&Q, 3.8 × 105 M-1 s-1 obtained for dimol quenching by DABCO in the NBS/ H 2O2 system Table 3, Agreement of values of k ΔQ determined in CL and in photosensitization experiments would quantitat
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Q determined in CL and in photosensitization experiments would quantitatively prove eq 4. However, because of the observed pH effect, it is open whether the agreement of the rate constants is possibly accidental.
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