Sensitive determination of radicals and paramagnetic species derived from medicinal and poisonous substances after changing valence states of metals contained

当药物和有毒物质活跃作用时，自由基和顺磁性中间体形成。在2003年至2005年的一系列研究中，我们开发了一种简单、快速、灵敏的方法来测定这些自由基和顺磁性金属螯合物。克利尔是一种掺假剂，可以掩盖尿液中的四氢大麻酚和吗啡。我们从clear的活性成分亚硝酸盐中产生NO自由基，并用DDC（二乙基二硫代氨基甲酸铁）络合物捕获NO。在不进行样品前处理的情况下，血浆、尿液和唾液中的亚硝酸盐在5 min内定量为NO-Fe-(DDC)_2，检出限为50 pg。钼（Mo）是人体必需的微量元素，其含量为140 ng/kg。当它作为酶的辅助因子时，它变成顺磁性的Mo^<5+>，可以被ESR检测到，尽管在其他报道中Mo^<5+>是不稳定的。我们成功地合成了一个新的稳定的Mo^<5+>配合物，并用ESR对其进行了检测。10 μl尿液中的Mo可在5 min内以50 pg的检出限进行定性。尿运气是一种含有四氢大麻酚和鸦片的掺杂剂，其活性成分是铬酸盐Cr^<6+>。Cr^<3+>不能用于此目的。已知Cr^<6+>会诱发癌症，而Cr^<3+>则不会。在这方面，需要形成Cr^<6+>和Cr^<3+>。以Cr^<6+>为原料制备出顺磁性Cr^<6+>(DDC)_4络合物，并对Cr^<6+>进行了灵敏的定量分析。为了测量微量的锰（Mn），我们采用了ESR方法，因为Mn^<2+>是顺磁性的。使用125 ppm的百草枯或将镁限制在推荐量的一半都不会影响组织锰水平。当两种治疗同时应用时，肝脏、肾脏和心脏的锰水平明显低于对照组。硫氰酸盐（SCN）是氰化物的主要代谢物，氰化物是一种著名的毒药。采用顺磁络合物Cu(SCN)_2（4-甲基吡啶）_2在苯中生成，然后用ESR法检测SCN的含量。根据本方法，可以在0.5 ml溶液中测定浓度为5μM ~ 2 mM的SCN。从血液、血浆、尿液和饮料中提取，回收率均在95%以上。叠氮化钠（N_3）在工业上用作汽车安全袋的炸药和诊断试剂的抗真菌剂。1998年，日本发生了几起叠氮化物中毒事件。方法是在苯中生成顺磁性配合物Cu(N_3)_2（4-甲基吡啶）_x，然后用ESR进行检测。少

Radicals and paramagnetic intermediates are formed when medicinal and poisonous substances are affecting actively. In our present series of study from 2003 to 2005, simple, rapid and sensitive methods have been developed for the determination of these radicals and paramagnetic metal-chelate complexes using electron spin resonance (ESR).1.Klear is an adulterant that conceal tetrahydrocannabinols and morphines present in urine. We produced NO radical from nitrite, the active component of Klear, and trapped NO with Fe-diethyldithiocarbamate(DDC) complex. Without sample pretretment, nitrite in plasma, urine or saliva was quantitated as NO-Fe-(DDC)_2 at the detection limit of 50 pg within 5 min.2.Molybdenum (Mo) is an essential trace element for human and is contained 140 ng/kg. When it works as cofactor of enzymes it becomes paramagnetic Mo^<5+> and detectable by ESR, although Mo^<5+> was unstable in other reports. We have succeeded in producing a new stable Mo^<5+> complex and detected it … More using ESR. Mo in 10 μl of urine could be quatitated at the detection limit of 50 pg within 5 min.3.Urine Luck is an adulterant that conceal tetrahydrocannabinols and opiates, and its active component is chromate Cr^<6+>. Cr^<3+> does not work for that purpose. Cr^<6+> is known to induce cancer while Cr^<3+> is not. In this respect, speciation of Cr^<6+> and Cr^<3+> is required. We produced paramagnetic Cr^<6+>(DDC)_4 complex from only Cr^<6+> and quantitated Cr^<6+> sensitively.4.To measure minute amounts of manganese (Mn), we applied ESR method because Mn^<2+> is paramagnetic. Tissue Mn levels were not affected by either dosing with paraquat at 125 ppm or restricting magnesium at half of recommended. When both treatments were applied together, Mn levels were lowered significantly from those of the control in liver, kidney and heart.5.Thiocyanate (SCN) is the main metabolite of cyanide, a famous poison. The procedure for the determination of SCN was based on the formation of a paramagnetic complex Cu(SCN)_2(4-methylpyridine)_2 in benzene, followed by its detection using ESR. According to the present method, SCN at concentrations from 5μM to 2 mM in 0.5 ml solution could be determined. The recoveries were more than 95% from blood, plasma and urine and beverages.6.Sodium azide (N_3) is used in industry as an explosive in automobile safety bags and an antifungal for diagnostic reagents. In 1998, several poisonous cases of azide occurred in Japan. The procedure was based on the formation of a paramagnetic complex Cu(N_3)_2(4-methylpyridine)_x in benzene, followed by its detection using ESR. Less