模型体系中PhIP、Norharman、Harman 3种杂环胺的形成与抑制

Formation and Inhibition of Three Heterocyclic Amines,PhIP,Norharman and Harman in a Model System

采用模型体系探讨2-氨基-1-甲基-6-苯基-咪唑并[4,5-b]吡啶(2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine,PhIP)、9H-吡啶并[3,4-b]吲哚(9H-pyrido[3,4-b]indole,norharman)、1-甲基-9H-吡啶并[3,4-b]吲哚(1-methyl-9H-pyrido[3,4-b]indole,harman)3种杂环胺的形成规律及抑制措施。结果表明:随着加热温度的升高与加热时间的延长,模型体系中PhIP、Norharman和Harman的形成量均不断增多,其中PhIP对加热温度较为敏感,100、125℃反应20 min不能形成PhIP,150℃加热时PhIP生成量开始逐渐增多,175~200℃加热时PhIP形成量急剧增加;单独加热色氨酸即能产生Norharman和Harman,加入葡萄糖时Norharman和Harman的形成量进一步提高;本研究建立的同时检测色氨酸、Norharman和Harman的色谱方法明确表明,色氨酸是Norharman和Harman的前体物;高良姜素及其类似物山柰酚和槲皮素均能在一定程度上减少PhIP的形成,但只有高良姜素能降低Harman和Norharman的形成量,而山柰酚和槲皮素不但没有抑制作用反而在一定程度上提高了Harman和Norharman的形成量,进一步证实β-咔啉类杂环胺形成的复杂性。

The formation mechanism of PhIP(2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine),norharman(9H-pyrido[3,4-b]indole)and harman(1-methyl-9H-pyrido[3,4-b]indole)were investigated in a model system and some measures to control these heterocyclic amines(HAs)were presented.Results showed that the fomation of PhIP,norharman and harman increased with increasing heating temperature and time.PhIP was particularly sensitive to heating temperature.No PhIP was detected in the system after being heated for 20 min at 100 or 125℃,while the formation rate began to increase at 150℃and increased sharply between 175 and 200℃.Norharman and harman were generated by heating tryptophan alone,but their formation increased when glucose was added.The simultaneous chromatographic detection of leucine,norharman and harman clearly indicated that tryptophan was a precursor of norharman and harman.Galangin and its analogues kaempferol and quercetin could decrease the formation of PhIP to certain degree,while only galangin could decrease the formation of norharman and harman.On the other hand,quercetin and kaempferol were found to increase the formation of norharman and harman,further indicating that HAs formation is a complex process.