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Volumn 111, Issue 20, 2007, Pages 4267-4273

On the effect of 1,4-diazabicyclo[2.2.2]octane on the singlet-oxygen dimol emission: Chemical generation of (1O2)2 in peroxide reactions

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; CHEMILUMINESCENCE; PARAFFINS; PYROLYSIS; REACTION KINETICS; SULFUR COMPOUNDS;

EID: 34250314529     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp070629p     Document Type: Article
Times cited : (30)

References (72)
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    • Schaap, A. P, Ed, Dowden, Hutchinson and Ross: Stroudsburg, PA
    • Singlet Molecular Oxygen; Schaap, A. P., Ed.; Dowden, Hutchinson and Ross: Stroudsburg, PA, 1976
    • (1976) Singlet Molecular Oxygen
  • 12
    • 13144281242 scopus 로고
    • Wasserman, H. H, Murray, R. W, Eds, Academic Press: New York
    • Organic Chemistry: Singlet Oxygen; Wasserman, H. H., Murray, R. W., Eds.; Academic Press: New York, 1979; Vol. 40.
    • (1979) Organic Chemistry: Singlet Oxygen , vol.40
  • 13
    • 0004007498 scopus 로고
    • Frimer, A.A, Ed, CRC: Boca Raton, FL
    • Singlet Oxygen; Frimer, A.A., Ed.; CRC: Boca Raton, FL, 1985.
    • (1985) Singlet Oxygen
  • 17
    • 0001252044 scopus 로고
    • Foote, C. S, Valentine, J. S, Greenberg, A, Liebman, J. F, Eds, Chapman and Hall: London
    • Foote, C. S.; Clennan, E. L. In Active Oxygen in Chemistry; Foote, C. S., Valentine, J. S., Greenberg, A., Liebman, J. F., Eds.; Chapman and Hall: London, 1995; Vol. 2, p 105.
    • (1995) Active Oxygen in Chemistry , vol.2 , pp. 105
    • Foote, C.S.1    Clennan, E.L.2
  • 47
    • 34250330719 scopus 로고    scopus 로고
    • Sharipov, G. L.; Kazakov, V. P.; Tolstikov G. A. Chemistry and chemiluminescence of 1,2-dioxetanes; Nauka: Moscow, 1990; in Russian.
    • Sharipov, G. L.; Kazakov, V. P.; Tolstikov G. A. Chemistry and chemiluminescence of 1,2-dioxetanes; Nauka: Moscow, 1990; in Russian.
  • 69
    • 34250318558 scopus 로고    scopus 로고
    • 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
    • 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.
  • 70
    • 34250306330 scopus 로고    scopus 로고
    • 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
    • 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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