Chu Y, Hurtubise R J
Department of Chemistry, University of Wyoming, Laramie 82071.
Photochem Photobiol. 1994 Jun;59(6):603-10. doi: 10.1111/j.1751-1097.1994.tb09663.x.
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-(N2-deoxyguanosyl-3'-phosphate)-7,8,9,10- tetrahydrobenzo(a)pyrene (BPDE-dG). The solid-matrix luminescence data were obtained for I-1 and BPDE-dG adsorbed on two different solid matrices, namely, 1% alpha-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 I-1 and BPDE-dG in contrast to the 1% alpha-CD/NaCl matrix. The BPDE-dG showed lower fluorescence quantum yields on the solid matrices compared to I-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 I-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.(ABSTRACT TRUNCATED AT 250 WORDS)
比较了苯并(a)芘-DNA加合物的两种重要产物的固体基质发光特性和几个计算得到的光物理参数。产物为苯并(a)芘-r-7,t-8,9,c-10-四氢四醇(I-1)和7R,8S,9S-三羟基-10R-(N2-脱氧鸟苷-3'-磷酸)-7,8,9,10-四氢苯并(a)芘(BPDE-dG)。在两种不同的固体基质上获得了I-1和BPDE-dG的固体基质发光数据,这两种固体基质分别是1%α-环糊精(CD)/NaCl和25%海藻糖/NaCl,且温度不同(93K和并296K)。与1%α-CD/NaCl基质相比,25%海藻糖/NaCl使I-1和BPDE-dG的荧光和磷光量子产率更高。与I-1相比,BPDE-dG在固体基质上的荧光量子产率较低。BPDE-dG较低的荧光量子产率归因于光诱导电子转移机制。与BPDE-dG在室温溶液中的荧光不同,BPDE-dG吸附在两种固体基质上时在室温下具有相当高的荧光量子产率。根据固体基质发光量子产率和固体基质发光寿命,计算并比较了许多光物理参数。注意到BPDE-dG和I-1在两种固体基质上的速率常数存在一些差异。例如,BPDE-dG在296K时,在25%海藻糖/NaCl存在下表现出内转换,但在93K时,在这种固体基质上未观察到内转换。同样,对于BPDE-dG,在296K和93K时,25%海藻糖/NaCl存在下的磷光速率常数非常小,但从三重态到基态的系间窜越速率常数非常大。(摘要截断于250字)