COMPARISON OF THE SOLID-MATRIX LUMINESCENCE PROPERTIES and PHOTOPHYSICAL PARAMETERS OF TWO PRODUCTS FROM BENZO(a)PYRENE-DNA ADDUCTS

Abstract The solid-matrix luminescence properties and several calculated photophysical parameters of two important products from the benzo(a)pyrene-DNA adducts were compared. The products were benzo(a)pyrene-r-7,t-8,9,c-10-tetrahydrotetrol (I-1) and 7R,8S,9S-trihydroxy-10R-(A^p-deoxyguanosyl-3'-phosphate)-7,8,9,1O-tetrahydroben-zo(a)pyrene (BPDE-dG). The solid-matrix luminescence data were obtained for 1–1and BPDE-dG adsorbed on two different solid matrices, namely, 1% a-cyclodextrin (CD)/NaCl and 25% trehalose/NaCl and at two different temperatures (93 K and 296 K). The 25% trehalose/NaCl gave higher fluorescence and phosphorescence quantum yields from both 1–1and BPDE-dG in contrast to the 1%α-CD/NaCl matrix. The BPDE-dG showed lower fluorescence quantum yields on the solid matrices compared to 1–1. The lower fluorescence quantum yields for BPDE-dG were attributed to a photoinduced electron transfer mechanism. In contrast to the room-temperature solution fluorescence of BPDE-dG, BPDE-dG gave rather high fluorescence quantum yields at room temperature when adsorbed on the two solid matrices. From solid-matrix luminescence quantum yields and solid-matrix luminescence lifetimes, many photophysical parameters were calculated and compared. Several differences among the rate constants were noted with the two solid matrices for BPDE-dG and 1–1. For example, BPDE-dG showed internal conversion at 296 K with 25% trehalose/NaCl, but no internal conversion was observed at 93 K with this solid matrix. Also, for BPDE-dG the phosphorescence rate constants at 296 K and 93 K. were very small with 25% trehalose/NaCl, but the intersystem crossing rate constants from the triplet state to the ground state were very large. The results from this work show how solid-matrix luminescence can be employed to obtain unique luminescence information from the 1–1and BPDE-dG systems.