Department of Chemistry and Biochemistry, Vanderbilt University, Nashville, Tennessee 37235-1822, USA.
Chem Res Toxicol. 2010 Jun 21;23(6):1076-88. doi: 10.1021/tx100053n.
2-Amino-3-methylimidazo[1,2-d]naphthalene (cIQ) is a carbocyclic analogue of the dietary carcinogen 2-amino-3-methylimidazo[4,5-f]quinoline (IQ) in which a naphthalene ring system replaces the quinoline unit of IQ. The activity of cIQ in Ames Salmonella typhimurium tester strain TA98 is known to be 4-5 orders of magnitude lower than IQ. cIQ undergoes efficient bioactivation with rat liver microsomes. The C8-dGuo adduct was formed when calf thymus DNA was treated with the N-hydroxy-cIQ metabolite and either acetic anhydride or extracts from cells that overexpress N-acetyl transferase (NAT). These studies indicate that bioactivation, the stability of the N-hydroxylamine ester, and the reactivity of the nitrenium ion with DNA of cIQ are similar to IQ and that none of these factors account for the differences in mutagenic potency of these analogues in Ames assays. Oligonucleotides were synthesized that contain the C8-dGuo adduct of cIQ in the frameshift-prone CG-dinucleotide repeat unit of the NarI recognition sequence. We have examined the in vitro translesion synthesis of this adduct and have found it to be a strong replication block to Escherichia coli DNA polymerase I, Klenow fragment exo(-) (Kf(-)), E. coli DNA polymerase II exo(-) (pol II(-)), and Sulfolobus solfataricus P2 DNA polymerase IV (Dpo4). Previous studies by Fuchs and co-workers identified E. coli pol II as the polymerase responsible for two-base deletions of the C8-dGuo adduct of N-acetyl-2-aminofluorene in the NarI sequence. Our observation that pol II is strongly inhibited by the C8-dGuo adduct of cIQ suggests that one of the other SOS inducible polymerases (E. coli pol IV or pol V) is required for its bypass, and this accounts for the greatly attenuated mutagenicity in the Ames assays as compared with IQ.
2-氨基-3-甲基咪唑[1,2-d]萘(cIQ)是一种饮食致癌物质 2-氨基-3-甲基咪唑[4,5-f]喹啉(IQ)的碳环类似物,其中萘环系统取代了 IQ 的喹啉单元。已知 cIQ 在鼠伤寒沙门氏菌 TA98 测试菌株中的致突变活性比 IQ 低 4-5 个数量级。cIQ 可与大鼠肝微粒体有效生物活化。当小牛胸腺 DNA 与 N-羟基-cIQ 代谢物以及乙酸酐或过表达 N-乙酰转移酶(NAT)的细胞提取物一起处理时,形成 C8-dGuo 加合物。这些研究表明,生物活化、N-羟胺酯的稳定性以及 cIQ 中氮烯离子与 DNA 的反应性与 IQ 相似,这些因素都不能解释这些类似物在 Ames 试验中的致突变效力差异。合成了含有 cIQ 的 C8-dGuo 加合物的寡核苷酸,该加合物位于 NarI 识别序列中易发生移码的 CG-二核苷酸重复单元中。我们已经研究了该加合物的体外转位合成,发现它是大肠杆菌 DNA 聚合酶 I、Klenow 片段 exo(-)(Kf(-))、大肠杆菌 DNA 聚合酶 II exo(-)(pol II(-))和 Solfolobus solfataricus P2 DNA 聚合酶 IV(Dpo4)的强烈复制阻断物。Fuchs 及其同事的先前研究确定大肠杆菌 pol II 是负责 NarI 序列中 N-乙酰-2-氨基芴的 C8-dGuo 加合物的双碱基缺失的聚合酶。我们观察到 pol II 被 cIQ 的 C8-dGuo 加合物强烈抑制,这表明 SOS 诱导的其他聚合酶之一(大肠杆菌 pol IV 或 pol V)需要其旁路,这解释了与 IQ 相比,在 Ames 试验中突变性大大减弱的原因。