Probe electrospray ionization coupled to a quadrupole time-Of-flight: A feasibility study for the detection of cocaine and its derivatives in oral fluid

IF 3.1 3区医学 Q2 CHEMISTRY, ANALYTICAL

Journal of pharmaceutical and biomedical analysis Pub Date : 2024-11-15 DOI:10.1016/j.jpba.2024.116568

Elisa Jousselin , Elies Zarrouk , Pauline Griffeuille , Sylvain Dulaurent , Souleiman El Balkhi , Franck Saint-Marcoux

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引用次数: 0

Abstract

Probe Electrospray Ionization (PESI) is an atmospheric pressure ionization method that can be directly coupled with a mass spectrometer to allow ultrafast analyses without chromatographic separation and with minimal sample preparation. Using the particular case of cocaine and its metabolites in human oral fluid, the main objective of the present study was to test the feasibility of a new hybrid system combining a PESI source and a quadrupole time-of-flight (QTOF). The best results were obtained for a sample preparation with a simple dilution of 100 µL of oral fluids in an ethanol / 10 mM ammonium formate buffer (50/50) and 10 µL deposited on a dedicated sample plate and introduced into the PESI source. For HRMS acquisition, an approach consisting in a full-mass scan (“untargeted approach” from 100 to 500 m/z; MS1) followed by a targeted scheduled MSMS acquisition (precursor ions of the 3 molecules of interest and their 3 internal standards; MS2) gave the best signals. The total time of analysis was 0.45 min and the method was validated according to ISO15189 standard for a 5–100 ng/mL range, including accuracy and precision (inter-day and intra-day precision and bias values were lower than 15 %), matrix effect, carryover and specificity (no interference with a mixture of 119 psychotropic drugs spiked at 1 mg/L). The LLOD values were 1 ng/mL for the 3 cocaine derivatives and 83 Driving Under the Influence of Drug (DUID) cases sent to our Lab for the determination of illicit drugs in oral fluid were analyzed using the PESI-QTOF method and compared to a LC-MS/MS method. A perfect agreement was observed between the 2 methods, whether the cases were positive or negative. Cocaine was detected in 51 out of these 83 real cases (61.6 %). BZE and EME were also simultaneously detected in 50 of them (98.5 %). This feasibility study reports the first analytical method based on a coupling of a PESI source to a QTOF mass spectrometer. Adding the major advantage of high specificity through HRMS is a step forward for PESI technology.

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探针电喷雾离子化与四极杆飞行时间相结合：检测口腔液中可卡因及其衍生物的可行性研究。

探针电喷雾离子化（PESI）是一种常压离子化方法，可直接与质谱仪联用，无需色谱分离，只需进行最少的样品制备即可进行超快速分析。本研究以人体口腔液中的可卡因及其代谢物为例，主要目的是测试将 PESI 源和四极杆飞行时间（QTOF）相结合的新型混合系统的可行性。样品制备的最佳结果是将 100 µL 口腔液在乙醇/10 mM 甲酸铵缓冲液（50/50）中进行简单稀释，然后将 10 µL 沉积在专用样品板上并导入 PESI 源。对于 HRMS 采集，先进行全质量扫描（从 100 m/z 到 500 m/z 的 "非目标方法"；MS1），然后再进行目标预定 MSMS 采集（3 个相关分子的前体离子及其 3 个内部标准；MS2），这样可以获得最佳信号。该方法的准确度和精密度（日间和日内精密度和偏差值均低于 15%）、基质效应、携带和特异性（在 119 种精神药物的混合物中以 1 mg/L 加标时无干扰）均符合 ISO15189 标准。使用 PESI-QTOF 方法分析了送往本实验室检测口服液中非法药物含量的 83 个受毒品影响驾驶（DUID）案例，并与 LC-MS/MS 方法进行了比较。无论是阳性还是阴性病例，两种方法的结果都完全一致。在这 83 个真实样本中，有 51 个样本（61.6%）检测出了可卡因。其中 50 例（98.5%）同时检测出 BZE 和 EME。本可行性研究报告首次提出了基于 PESI 源与 QTOF 质谱仪耦合的分析方法。通过 HRMS 增加高特异性的主要优势是 PESI 技术向前迈出的一步。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of pharmaceutical and biomedical analysis 医学-分析化学

CiteScore

6.70

自引率

5.90%

发文量

588

审稿时长

37 days

期刊介绍： This journal is an international medium directed towards the needs of academic, clinical, government and industrial analysis by publishing original research reports and critical reviews on pharmaceutical and biomedical analysis. It covers the interdisciplinary aspects of analysis in the pharmaceutical, biomedical and clinical sciences, including developments in analytical methodology, instrumentation, computation and interpretation. Submissions on novel applications focusing on drug purity and stability studies, pharmacokinetics, therapeutic monitoring, metabolic profiling; drug-related aspects of analytical biochemistry and forensic toxicology; quality assurance in the pharmaceutical industry are also welcome. Studies from areas of well established and poorly selective methods, such as UV-VIS spectrophotometry (including derivative and multi-wavelength measurements), basic electroanalytical (potentiometric, polarographic and voltammetric) methods, fluorimetry, flow-injection analysis, etc. are accepted for publication in exceptional cases only, if a unique and substantial advantage over presently known systems is demonstrated. The same applies to the assay of simple drug formulations by any kind of methods and the determination of drugs in biological samples based merely on spiked samples. Drug purity/stability studies should contain information on the structure elucidation of the impurities/degradants.