Paul Buddha D
Division of Forensic Toxicology, Office of Armed Forces Medical Examiner, Armed Forces Institute of Pathology, Rockville, Maryland 20850, USA.
J Anal Toxicol. 2004 Oct;28(7):599-608. doi: 10.1093/jat/28.7.599.
Six separate methods to detect oxidants in urine were developed. The presence of the oxidants was established by initial oxidation of ferrous to ferric ion and detecting the ferric by chromogenic oxidation or complex formation. The reagents for chromogenic oxidation were N,N-dimethylamoino-1,4-phenylenediamine (DMPDA), 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid (ABTS), and 2-amino-p-cresol (APC), and the reagents for the chromogenic complex were xylenol orange (XO), 8-hydroxy-7-iodo-5-quinolinesulfonic acid (HIQSA), and 4,5-dihydroxy-1,3-benzene-di-sulfonic acid (HBSA). All methods showed comparable results when tested for ferric, chromate, permanganate, oxychloride, hydrogen peroxide, oxone, tert-butylhydroperoxide, and cumenehydroperoxide at a concentration of 1.0 mmol/L in water (CV < 7%). The nitrite results are comparable only with DMPDA and APC. Periodate responded to the highest oxidation number (ON = 8) by chromogenic oxidation but lowest (ON = 2) by the chromogenic complex. The iodate responded only to the chromogenic oxidation with ON = 6. The linearity of the procedures was established by chromate in water. The linear concentrations were 0.09-12.00 mE/L for DMPDA, ABTS, APC, and HBSA and 0.09-6.00 mE/L for XO and HIQSA. In all methods, the correlation coefficients were > or = 0.9991 and precisions were within +/- 5.6%. The methods were used to test oxidants in 238 urine specimens. The chromate at 3.0 mE/L in water was used as standard. The correlation coefficients of 0.9600-0.9853 and the ANOVA test (F = 0.90, F(critical) = 2.22 at P(0.48)) indicated that the methods correlated well. The median concentration of oxidants in the specimens was 0.21 mE/L with an average and standard deviation of 0.62 +/- 1.19 (range 0.04-8.83 mE/L). When Grubbs' statistical test was applied to the specimen results, no specimen was found to be outlier or could be considered as adulterated. The Grubbs' test also revealed that the threshold concentration to identify urine adulteration was 29 mE/L at confidence level of 99%.
开发了六种单独检测尿液中氧化剂的方法。通过将亚铁离子初步氧化为铁离子，并通过显色氧化或络合物形成来检测铁离子，从而确定氧化剂的存在。用于显色氧化的试剂有N,N-二甲基氨基-1,4-苯二胺（DMPDA）、2,2'-联氮-双（3-乙基苯并噻唑啉-6-磺酸）（ABTS）和2-氨基对甲酚（APC），用于显色络合物的试剂有二甲酚橙（XO）、8-羟基-7-碘-5-喹啉磺酸（HIQSA）和4,5-二羟基-1,3-苯二磺酸（HBSA）。当在水中对浓度为1.0 mmol/L的铁离子、铬酸盐、高锰酸盐、次氯酸盐、过氧化氢、过氧单磺酸钾、叔丁基过氧化氢和氢过氧化异丙苯进行测试时，所有方法都显示出可比的结果（变异系数<7%）。亚硝酸盐结果仅与DMPDA和APC可比。高碘酸盐通过显色氧化对最高氧化数（氧化数=8）有响应，但通过显色络合物对最低氧化数（氧化数=2）有响应。碘酸盐仅对氧化数为6的显色氧化有响应。该方法的线性通过水中的铬酸盐确定。DMPDA、ABTS、APC和HBSA的线性浓度为0.09 - 12.00 mE/L，XO和HIQSA的线性浓度为0.09 - 6.00 mE/L。在所有方法中，相关系数≥0.9991，精密度在±5.6%以内。这些方法用于检测238份尿液标本中的氧化剂。将水中3.0 mE/L的铬酸盐用作标准。相关系数为0.9600 - 0.9853，方差分析测试（F = 0.90，P(0.48)时F临界值 = 2.22）表明这些方法相关性良好。标本中氧化剂的中位数浓度为0.21 mE/L，平均值和标准差为0.62±1.19（范围为0.04 - 8.83 mE/L）。当对标本结果应用格拉布斯统计检验时，未发现任何标本为异常值或可被视为掺假。格拉布斯检验还表明，在99%置信水平下识别尿液掺假 的阈值浓度为29 mE/L。
