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纤维喷雾电离质谱在法医化学中的应用:滥用药物的筛选和尿液中可卡因的直接测定。

Fiber spray ionization mass spectrometry in forensic chemistry: A screening of drugs of abuse and direct determination of cocaine in urine.

机构信息

Laboratório de Petroleômica e Química Forense, Departamento de Química, Universidade Federal do Espírito Santo, Vitória, ES, 29075-910, Brazil.

Instituto Federal do Espírito Santo, São Mateus, ES, 29932-540, Brazil.

出版信息

Rapid Commun Mass Spectrom. 2020 Sep;34 Suppl 3:e8747. doi: 10.1002/rcm.8747. Epub 2020 May 10.

Abstract

RATIONALE

Ambient mass spectrometry techniques are much required in forensic chemistry to evaluate evidence with low analytical interference, high confidence, and accuracy. However, traditional methodologies, such as paper spray ionization, have been shown to present low sensitivity in the analysis of illicit drugs from biological matrices.

METHODS

Fiber spray ionization mass spectrometry (FSI-MS) was developed using a capillary polypropylene (PP) hollow fiber. Seized samples of drugs, i.e. a tablet, blotter paper, hashish, and cocaine powder, were analyzed. Cocaine was quantified from whole urine by dipping the fiber directly into solution. FSI-MS was tested for the analysis of a sample of urine obtained from a drug abuse suspect.

RESULTS

The FSI(+) analysis showed the detection of different types of synthetic drugs in tablet and blotter paper samples, e.g. amphetamine, cathinones, phenethylamines, and opioids, while pure cocaine and different types of coca alkaloids were identified from cocaine powder with good sensitivity and high mass accuracy. The hashish analysis by FSI(-) revealed signals of cannabinoids, cannabinoid acids, and cannabinoid derivatives, detected mainly as [M - H] ions or chlorine adducts [M + Cl] . The quantification of cocaine in whole urine showed good sensitivity and precision with limits of detection and quantification of 5.16 and 17.21 ng/mL, respectively, linearity above 0.999, and relative standard deviation below 2.71%. The evaluation of seized sample of urine showed the detection of cocaine with relative ion intensity greater than 36%, as well as the metabolites benzoylecgonine and cocaethylene with a relative intensity of 1.4% and 6%, respectively.

CONCLUSIONS

The developed FSI-MS method has the potential to be applied to forensic sample evaluation as well as to determine illicit drugs from biological matrices in toxicological analysis. The use of a capillary PP fiber has advantages as an extractor agent and ionizing substrate, and also the feature of it being dipped directly into the sample, thus preserving the integrity of the sample, which makes this a very promising ambient mass spectrometry method and relevant to forensic chemistry.

摘要

原理

环境质谱技术在法医化学中非常需要,以评估具有低分析干扰、高置信度和准确性的证据。然而,传统方法,如纸喷雾电离,已被证明在分析生物基质中的非法药物时灵敏度较低。

方法

纤维喷雾电离质谱(FSI-MS)使用毛细管聚丙烯(PP)中空纤维开发。对缴获的药物样品,即片剂、浸滤纸片、大麻和可卡因粉末进行分析。通过将纤维直接浸入溶液中,从全尿中定量可卡因。测试了 FSI-MS 对从药物滥用嫌疑犯尿液中获得的样品的分析。

结果

FSI(+)分析显示,在片剂和浸滤纸片样品中检测到不同类型的合成药物,如安非他命、苯丙胺、苯乙胺和阿片类药物,而从可卡因粉末中则鉴定出纯可卡因和不同类型的古柯生物碱,具有良好的灵敏度和高质量精度。FSI(-)分析显示大麻素、大麻素酸和大麻素衍生物的信号,主要以[M-H]离子或氯加合物[M+Cl]形式检测。全尿中可卡因的定量具有良好的灵敏度和精密度,检测限和定量限分别为 5.16 和 17.21ng/mL,线性度大于 0.999,相对标准偏差小于 2.71%。对缴获尿液样品的评估显示,可卡因的检测相对离子强度大于 36%,以及代谢物苯甲酰古柯碱和古柯乙基的相对强度分别为 1.4%和 6%。

结论

所开发的 FSI-MS 方法具有应用于法医样品评估以及在毒理学分析中从生物基质中确定非法药物的潜力。使用毛细管 PP 纤维作为提取剂和电离基质具有优势,并且还可以直接浸入样品中,从而保持样品的完整性,这使得这是一种非常有前途的环境质谱方法,与法医化学相关。

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