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 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 (US)
Pages (from-to)778-788
Number of pages11
JournalChemical Research in Toxicology
Volume12
Issue number9
DOIs
StatePublished - Oct 5 1999

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Estuaries
Deoxyguanosine
Epoxy Compounds
Spectrum Analysis
Fluorescence
Nuclear magnetic resonance
Spectroscopy
Fast Atom Bombardment Mass Spectrometry
Dimethylformamide
Stereochemistry
Stereoisomerism
Isomers
Mass spectrometry
High Pressure Liquid Chromatography
Atoms
dibenzo(a,l)pyrene 11,12-dihydrodiol

ASJC Scopus subject areas

  • Toxicology

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Structure elucidation of the adducts formed by fjord region dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxides with deoxyguanosine. / Li, Kai Ming; George, Mathai; Gross, Michael L.; Lin, Cheng Huang; Jankowiak, Ryszard; Small, Gerald J.; Seidel, Albrecht; Kroth, Heiko; Rogan, Eleanor G; Cavalieri, Ercole.

In: Chemical Research in Toxicology, Vol. 12, No. 9, 05.10.1999, p. 778-788.

Research output: Contribution to journalArticle

Li, Kai Ming ; George, Mathai ; Gross, Michael L. ; Lin, Cheng Huang ; Jankowiak, Ryszard ; Small, Gerald J. ; Seidel, Albrecht ; Kroth, Heiko ; Rogan, Eleanor G ; Cavalieri, Ercole. / Structure elucidation of the adducts formed by fjord region dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxides with deoxyguanosine. In: Chemical Research in Toxicology. 1999 ; Vol. 12, No. 9. pp. 778-788.
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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.",
author = "Li, {Kai Ming} and Mathai George and Gross, {Michael L.} and Lin, {Cheng Huang} and Ryszard Jankowiak and Small, {Gerald J.} and Albrecht Seidel and Heiko Kroth and Rogan, {Eleanor G} and Ercole Cavalieri",
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T1 - Structure elucidation of the adducts formed by fjord region dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxides with deoxyguanosine

AU - Li, Kai Ming

AU - George, Mathai

AU - Gross, Michael L.

AU - Lin, Cheng Huang

AU - Jankowiak, Ryszard

AU - Small, Gerald J.

AU - Seidel, Albrecht

AU - Kroth, Heiko

AU - Rogan, Eleanor G

AU - Cavalieri, Ercole

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N2 - (±)-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.

AB - (±)-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.

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