Evaluation of interaction between hemoglobin and oxime-type carbamate pesticides.
Evaluation of interaction between hemoglobin and oxime-type carbamate pesticides.
复制标题
血红蛋白与肟型氨基甲酸酯农药之间相互作用的评价。
DOI：
10.1021/acs.chemrestox.2c00092
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发表时间：
2022
影响因子：
4.1
通讯作者：
H. Iwase and Y. Ogra
中科院分区：
文献类型：
--
作者：
Y. Yamagishi;S. Nagasawa;H. Iwase and Y. Ogra
已在许多意外接触或自杀的致死案例中检测到具有肟基部分的肟型氨基甲酸酯类杀虫剂，如灭多威、丁甲硫磷、灭多威、恶霉威和硫氰菊酯。在法医毒理学中，准确测定血液中的农药浓度是证明肟型氨基甲酸酯类农药中毒致死的必要条件。然而，尸检时血液中致命的杀虫剂浓度与死亡时不同。在这项研究中，我们发现HB以依赖于温度的方式对肟类氨基甲酸酯类农药进行分解。灭多威、敌百威、恶草胺和硫代呋喃分解的机理涉及与Hb中的氨基酸形成加合物。至于丁羧硫磷，它的分解包括游离形式的氧化和与Hb中的氨基酸形成加合物。用四极杆飞行时间质谱仪获得的质谱图表明，在与灭多威、敌百威、恶菌灵和硫氰菊酯孵育的HB溶液中，生成了WCAR-加合物和VCAR-加合物等氨基甲酰化氨基酸加合物，而在与丁羧磷孵育的HB溶液中，生成了烷基化氨基酸加合物，如WCAR-加合物和VCAR加合物。这些结果表明，杀菌威、丁羧硫磷、灭多威、恶菌灵和硫氰菊酯是由HB在死后发生变化的。
Oxime-type carbamate pesticides having an oxime moiety such as aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are widely used and have been detected in many fatal cases of accidental exposure or suicide. In forensic toxicology, the accurate determination of blood pesticide concentration is obligatory to prove death by oxime-type carbamate pesticide poisoning. However, the fatal pesticide concentration in blood at autopsy differs from that at the time of death. In this study, we found that oxime-type carbamate pesticides were decomposed by Hb in a temperature-dependent fashion. The mechanism underlying methomyl, aldicarb, oxamyl, and thiofanox decomposition involves the formation of adducts with the amino acids in Hb. With regard to butocarboxim, its decomposition involves the oxidation of the free form and the formation of adducts with the amino acids in Hb. The mass spectra obtained by liquid chromatography quadrupole time-of-flight mass spectrometry revealed that carbamylated amino acid adducts such as Wcar-adduct and Vcar-adduct were formed in Hb solution incubated with methomyl, aldicarb, oxamyl, and thiofanox, whereas alkylated amino acid adducts such as Walkyl-adduct were formed in Hb solution incubated with butocarboxim. These results indicate that aldicarb, butocarboxim, methomyl, oxamyl, and thiofanox are post-mortem changed by Hb.