Synthesis and structure determination of the adducts formed by electrochemical oxidation of the potent carcinogen dibenzo[a,I]pyrene in the presence of nucleosides.
Synthesis and structure determination of the adducts formed by electrochemical oxidation of the potent carcinogen dibenzo[a,I]pyrene in the presence of nucleosides.
复制标题
在核苷存在下，强致癌物二苯并[a,I]芘的电化学氧化形成的加合物的合成和结构测定。
DOI：
10.1021/tx00034a026
复制
发表时间：
1993
影响因子：
4.1
通讯作者：
Gross,ML
中科院分区：
文献类型：
--
作者：
RamaKrishna,NV;Padmavathi,NS;Cavalieri,EL;Rogan,EG;Cerny,RL;Gross,ML
Because dibenzo [o, l] pyrene (DBP) is the most potent known carcinogenic aromatic hydro-carbon, reference adducts formed by reactionof deoxyribonucleosides with electrophilic intermediates of DBP are essential for identifying the structuresof adducts formedin biological systems. Electrochemical oxidation of DBP in the presence of nucleosides leads to adducts from DBP,+. When 6.8 equiv of charge are consumed, three adducts are formed with dG: 7-(DBP-10-yl) Gua (89%), 8-(DBP-10-yl) dG (2%), and 8-(DBP-10-yl) Gua (2%). With 10 equiv of charge, however, only two adducts are formed: 7-(DBP-10-yl) Gua (89%) and 8-(DBP-10-yl) Gua (4%). Anodic oxidation of 8-(DBP-10-yl) dG yields 8-(DBP-10-yl) Gua. Anodic oxidation of DBP in the presence of G produces 7-(DBP-10-yl) Gua (27%) and 8-(DBP-10-yl) G (9%). Anodic oxidation of DBP in the presence of dA affords two adducts, 2V6-(DBP-10-yl) dA (28%) and 7-(DBP-10-yl) Ade (12%), whereas anodic oxidation in the presence of A produces only N6-(DBP-10-yl) A (24%). The structuresof the adducts were elucidated by using UV, NMR, and MS. Formation of these adducts demonstrates that DBP*+ reacts at C-10 with nucleophiles. The most reactive nucleophilic groups for the Gua moiety are the N-7 and C-8, whereas for the Ade moiety they are N-7 and the 6-amino group.
