Structure elucidation of the adducts formed by fjord region dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxides with deoxyguanosine

Kai Ming Li, Mathai George, Michael L. Gross, Cheng Huang Lin, Ryszard Jankowiak, Gerald J. Small, Albrecht Seidel, Heiko Kroth, Eleanor G. Rogan, Ercole L. Cavalieri

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Abstract

(±)-anti-Dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxide {(±)- anti-DB[a,l]PDE} was reacted with deoxyguanosine (dG) in dimethylformamide at 100 °C for 30 min, and two sets of adducts were isolated: a mixture of (±)-anti-cis- and -trans-N2dG (43%) and a mixture of (±)anti-cis- and - trans-N7Gua (45%). Both are mixtures of four stereoisomers that cannot be separated by HPLC. Similarly, (±)-syn-DB[a,l]PDE was reacted with dG under the same conditions, and (±)-syn-cis- and -trans-N2dG (38%) and (±)-syn- cis- and -trans-N7Gua (59%) were obtained. The structures of the adducts were determined by a combination of NMR and fast atom bombardment mass spectrometry. By reacting (-)-anti-DB[a,l]PDE or (+)-syn-DB[a,l]PDE with dG under the same conditions, however, optically pure N2dG and N7Gua isomers were obtained: (-)-anti-cis-N2dG (12%), (-)-anti-trans-N2dG (17%), (-)- anti-trans-N7Gua (43%), (+)-syn-cis-N2dG (7%), (+)-syn-trans-N2dG (3%), (+)-syn-cis-N7Gua (36%), and (+)-syntrans-N7Gua (22%). The structures of the optically pure adducts were assigned by NMR. syn-and anti-DB[a,l]PDE-N2dG adducts can be distinguished by fluorescence line-narrowing spectroscopy (FLNS). Moreover, distinction between cis- and trans-stereochemistry of the adducts is also straightforward by FLNS, because the FLN spectra for the four DB[a,l]PDEN2dG adducts, anti-cis, anti-trans, syn-cis, and syn-trans, are spectroscopically unique.

Original languageEnglish
Pages (from-to)778-788
Number of pages11
JournalChemical Research in Toxicology
Volume12
Issue number9
DOIs
Publication statusPublished - 1999 Oct 5

ASJC Scopus subject areas

  • Toxicology

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    Li, K. M., George, M., Gross, M. L., Lin, C. H., Jankowiak, R., Small, G. J., Seidel, A., Kroth, H., Rogan, E. G., & Cavalieri, E. L. (1999). Structure elucidation of the adducts formed by fjord region dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxides with deoxyguanosine. Chemical Research in Toxicology, 12(9), 778-788. https://doi.org/10.1021/tx980234k