TY - JOUR
T1 - Chemiluminescence Mechanism and Quantum Yield of Synthetic Vinylpyrene Analogues of Benzo[a]pyrene-7,8-dihydrodiol
AU - Thompson, Ambler
AU - Seliger, H. H.
AU - Lever, John R.
AU - Canella, Karen A.
AU - Miura, Kyo
AU - Posner, Gary H.
PY - 1986/7/1
Y1 - 1986/7/1
N2 - We have previously reported that the dioxetane chemiluminescence (CL) of the proximate carcinogenic metabolite (±)-trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene (7,8-Diol) could be produced by free singlet oxygen (1O2) in solution. We now report that the trans-1-(2-methoxyvinyl)pyrene (t-MVP) model chemical analogue, in which an ene reaction is prevented, has a CL quantum yield ϕCL(t-MVP) of 0.003, 180 times that of 7,8-diol. The CL emission spectrum of t-MVP was identical with the fluorescence emission spectrum of the dioxetane decomposition product, pyrene-1-carboxaldehyde (6 in Scheme II), which was isolated in 10% yield in 1O2 reactions. The solvent dependencies of ϕCL t-MVP of dioxetanes parallel the fluorescence quantum yield (ϕFluor) of 6 and the CL yield from dioxetanes of 7,8-Diol in these same solvents. This dioxetane CL of the t-MVP analogue supports the originally proposed dioxetane CL mechanism of 7,8-Diol. The limiting factor in 7,8-Diol CL appears to be the low chemical yield for formation of the 9,10-dioxetane.
AB - We have previously reported that the dioxetane chemiluminescence (CL) of the proximate carcinogenic metabolite (±)-trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene (7,8-Diol) could be produced by free singlet oxygen (1O2) in solution. We now report that the trans-1-(2-methoxyvinyl)pyrene (t-MVP) model chemical analogue, in which an ene reaction is prevented, has a CL quantum yield ϕCL(t-MVP) of 0.003, 180 times that of 7,8-diol. The CL emission spectrum of t-MVP was identical with the fluorescence emission spectrum of the dioxetane decomposition product, pyrene-1-carboxaldehyde (6 in Scheme II), which was isolated in 10% yield in 1O2 reactions. The solvent dependencies of ϕCL t-MVP of dioxetanes parallel the fluorescence quantum yield (ϕFluor) of 6 and the CL yield from dioxetanes of 7,8-Diol in these same solvents. This dioxetane CL of the t-MVP analogue supports the originally proposed dioxetane CL mechanism of 7,8-Diol. The limiting factor in 7,8-Diol CL appears to be the low chemical yield for formation of the 9,10-dioxetane.
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U2 - 10.1021/ja00275a040
DO - 10.1021/ja00275a040
M3 - Article
AN - SCOPUS:2042480811
SN - 0002-7863
VL - 108
SP - 4498
EP - 4504
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 15
ER -