Letter: Differentiation of Isomeric Mercapturic Acid Pathway Metabolites of Benzo[a]pyrene

Abstract

Isomeric forms of the mercapturic acid pathway metabolites of benzo[a]pyrene (BP) can be differentiated by positive-ion electrospray collision-induced dissociation (CID) mass spectrometry at the nanogram level. The metabolite (±)-r-7,t-8-dihydroxy-t-9,10-epoxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE), conjugated at position 10 (bay region) with cysteine, fragments to give characteristic ions at m/z 303 corresponding to a BP-triol cation, these ions are not observed in the CID spectra of BPDEs conjugated at position 7 (non-bay region).

Keywords

benzo[a]pyrene mercapturic acid metabolites diolepoxides electrospray tandem mass spectrometry mass spectrometry

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References

Phillips

D.H.

, Nature 303, 468 (1983).

Jernström

and Graslund

, Biophysical Chemistry 49, 185 (1994).

Chasseaud

L.F.

, in Glutathione: Metabolism and Function, Ed by Arias

I. M.

and Jakoby

W. B.

Ravan Press, New York, pp. 77–114 (1976).

Egestad

Pettersson

Sjövall

Rafter

Hyvönen

and Gustafsson

J.-A.

, Biomed. Chromatogr. 2, 120 (1987).

Yang

Egestad

and Rafter

, Proceeding of the VIIIth International Symposium on Microsomes and Drug Oxidations, Karolinska Institute, Stockholm, Sweden, June 25–29 (1990).

Yang

Griffiths

W. J.

Sjövall

Gustafsson

J.-Å.

and Rafter

, J. Am. Soc. Mass Spectrom. 8, 50 (1997).

Yang

Egestad

Jernström

Sjövall

Gustafsson

J.-Å.

and Rafter

, Rapid Commun. Mass Spectrom. 5, 499 (1991).

Bateman

R.H.

Green

M.R.

Scott

and Clayton

, Rapid Commun. Mass Spectrom. 9, 1227 (1995).

Roepstorff

and Fohlman

, Biomed. Mass Spectrom. 11, 601 (1984).

10.

RamaKrishna

N.V.S.

Gao

Padmavathi

N.S.

Cavalieri

E.L.

Rogan

E.G.

Cerny

R.L.

and Gross

M.L.

, Chem. Res. Toxicol. 5, 293 (1992).

11.

Zaia

and Biemann

, J. Am. Soc. Mass Spectrom. 5, 649 (1994).

12.

Branco

Chiarelli

M.P.

Lay

J. O.

Jr. and Beland

F.A.

, J. Am. Soc. Mass Spectrom. 6, 248 (1995).

13.

Lowe

J.P.

and Silverman

R.D.

, J. Mol. Struct. (Theochem) 179, 47 (1988).

14.

Lehr

R.E.

Kumar

Levin

Wood

A.W.

Chang

R.L.

Conney

A.H.

Yagi

Sayer

J.M.

and Jerina

D.M.

, in Polycyclic Hydrocarbons and Carcinogenesis, Ed. by Harvey

R.G.

ACS Symposium Series 283, American Chemical Society, Washington DC, p. 63 (1985).

15.

Lowe

J.P.

and Silverman

R.D.

, J. Am. Chem. Soc. 103, 2852 (1981).