Heterogeneous distributions and dispersive photodissociation rates of benzo[a]pyrene diol-epoxide enantiomer-DNA and -poly(dG-dC).poly(dG-dC) adducts.
Two types of heterogeneity of adducts are illustrated and discussed utilizing non-line narrowed (S2----S0 laser excitation) and line-narrowed (excitation into the (0,0) origin band) fluorescence spectra at low temperatures. The first type (type A) is due to structurally distinct and/or energetically inequivalent conformers. The second one (type B) is provided by an inhomogeneous environment of DNA and polynucleotides. In light of the above, the non-exponential photodissociation kinetics of the (+/-)-anti-BPDE-DNA and -polynucleotide adducts have been reanalyzed in terms of a dispersive first order chemical reaction, where the inhomogeneous effects are explicitly included. It is demonstrated that the DNA structure shows considerable inhomogeneous broadening, and that type B heterogeneity is responsible for the dispersive photodissociation process. The latter is accounted for by a Gaussian distribution of activation energies, with the center of the distribution at approximately 600 meV and the full width at half-maximum equal to approximately 50 meV (approximately 2 kT). Photolabile (+/-)-anti-BPDE-DNA and -polynucleotide adducts are identified as quasi-intercalated (site I) (+)- and (-)-cis-BPDE. The calculated concentrations of cis-BPDE adducts in DNA and polynucleotides from the kinetic data are in very good agreement with the cis-BPDE adduct concentrations obtained from the spectral and/or chemical analysis. The average photodissociation rate and the photodissociation quantum yield of cis- and trans-BPDE adducts are also estimated.
Jankowiak
R
R
Ames Laboratory, U.S. Department of Energy, Iowa State University, Ames 50011.
D015123:7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D010777:Photochemistry; D011089:Polydeoxyribonucleotides / Q000737:chemistry*; D013237:Stereoisomerism
D011089:Polydeoxyribonucleotides; C019530:poly(dC-dG); D015123:7,8-Dihydro-7,8-dihydroxybenzo(a)pyrene 9,10-oxide; D004247:DNA