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

改变所含金属价态后，灵敏测定源自药用和有毒物质的自由基和顺磁性物质

• 批准号: 15590576
• 负责人: MINAKATA Kayoko
• 金额: $ 2.05万
• 依托单位: Hamamatsu University School of Medicine
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15590576/
• 关键词: electron spin resonance; NO radical; molybdenum; chromate; manganese; paraquat; thiocyanate; sodium azide; イオンスプレー質量分析; Urine Luck; ジエチルジチオカルバミン酸; クエン酸; クロム; スーパーオキサイド; マグネシウム; ESR法; 亜硝酸; 硝酸; 鉄; シュウ酸

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

当药物和有毒物质作用时，形成自由基和顺磁性中间体。在我们目前的系列研究从2003年到2005年，简单，快速和灵敏的方法已经开发出用于测定这些自由基和顺磁性金属螯合物的电子自旋共振（ESR）。我们从Klear的活性成分亚硝酸根中产生NO自由基，并用Fe-二乙基二硫代氨基甲酸盐（DDC）络合物捕获NO。在不经样品前处理的情况下，血浆、尿液和唾液中的亚硝酸盐以NO-Fe-（DDC）_2形式定量，检测限为50 pg，测定时间为5 min。当它作为酶的辅因子时，它变成了顺磁性的Mo^<5+>，可以用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种新的稳定的Mo^<5+>配合物，并对其进行了检测 ...更多信息 使用ESR。10 μl尿液中钼的检出限为50 pg，测定时间为5 min。3.尿乐克是一种隐藏四氢大麻酚和阿片类药物的掺假物，其有效成分为铬酸根Cr^<6+>。Cr^<3+>不适用于该目的。已知Cr^<6+>会诱发癌症，而Cr^<3+>则不会。在这方面，需要对Cr^<6+>和Cr^<3+>进行形态分析。4.由于Mn^<2 +>是顺磁性的，我们采用ESR方法测定微量锰（Mn）。组织锰水平不受百草枯剂量为125 ppm或限制镁为推荐量的一半的影响。当两种处理同时施用时，肝脏、肾脏和心脏中的Mn含量均显著低于对照组。5.硫氰酸盐（SCN）是氰化物的主要代谢产物。SCN在苯中与Cu（SCN）_2（4-甲基吡啶）_2形成顺磁性配合物，用ESR法测定。根据本方法，可以在0.5ml溶液中测定浓度为5μM至2 mM的SCN。在血液、血浆、尿液和饮料中的回收率均在95%以上。6.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。该方法是基于在苯中形成顺磁性配合物Cu（N_3）_2（4-甲基吡啶）_x，然后用ESR检测。少

项目成果

Determination of platinum derived from cisplatin in human tissues using electrospray ionization mass spectrometry

使用电喷雾电离质谱法测定人体组织中顺铂衍生的铂

• 发表时间: 2006
• 期刊: Journal of Chromatography B (in press)
• 作者: K.Sakurada;K.Matsubara;K.Shimizu;H.Shiono;Y.Seto;K.Tsuge;M.Yoshino;I.Sakai;H.Mukoyama;T.Takatori;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata
• 通讯作者: Kayoko Minakata

The restriction of all minerals in the diet enhancing paraquat toxicity is regarded primarily as the shortage of Mg

饮食中所有矿物质的限制会增加百草枯的毒性，这主要被认为是由于镁的缺乏

• 发表时间: 2003
• 期刊: Legal Medicine 5
• 作者: Mori M.;et al.;Kayoko Minakata;Takahashi M et al.;Kayoko Minakata
• 通讯作者: Kayoko Minakata

Manganese levels in tissues of paraquat dosed and/or magnesium restricted rats measure by an electron spin resonance method

通过电子自旋共振法测量百草枯给药和/或镁限制大鼠组织中的锰水平

• 发表时间: 2004
• 期刊: Japanese Journal of Forensic Toxicology 22
• 作者: K.Sakurada;K.Matsubara;K.Shimizu;H.Shiono;Y.Seto;K.Tsuge;M.Yoshino;I.Sakai;H.Mukoyama;T.Takatori;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;南方 かよ子;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata;Kayoko Minakata
• 通讯作者: Kayoko Minakata

Kayoko Minakata: "Determination of nitrite in biological fluids by use of electron spin resonance"Anal.Biochem.. 325. 168-170 (2004)

Kayoko Minakata：“利用电子自旋共振测定生物体液中的亚硝酸盐”Anal.Biochem.. 325. 168-170 (2004)

Kayoko Minakata: "The restriction of all minerals in the diet enhancing paraquat toxicity is regarded primarily as the shortage_of Mg"Legal Medicine. 5. S110-S112 (2003)

Kayoko Minakata：“饮食中所有矿物质的限制会增加百草枯的毒性，这主要被视为镁的短缺”法律医学。