Open Port Probe Sampling Interface for the Direct Coupling of Biocompatible Solid-Phase Microextraction to Atmospheric Pressure Ionization Mass Spectrometry
Open Port Probe Sampling Interface for the Direct Coupling of Biocompatible Solid-Phase Microextraction to Atmospheric Pressure Ionization Mass Spectrometry
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DOI：
10.1021/acs.analchem.6b04737
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发表时间：
2017-04-04
影响因子：
7.4
通讯作者：
Pawliszyn, Janusz
中科院分区：
文献类型：
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作者：
Gomez-Rios, German Augusto;Liu, Chang;Pawliszyn, Janusz
近年来，固相微萃取 (SPME) 和质谱 (MS) 的直接耦合显示出与直接进样至 MS 相比，其在改善定量限、加速分析通量和减少潜在基质效应方面的巨大潜力。在本研究中，我们引入开放端口探针 (OPP) 作为一个强大的接口，将生物相容性 SPME (Bio-SPME) 纤维耦合到 MS 系统以进行直接电喷雾电离。与基于 LC-MS 的方法相比，所提出的设计对仪器前端的改动极小，并且提供了更好的灵敏度、简单性、速度、更广泛的化合物覆盖范围和高通量。成功定量测定人尿液中的克伦特罗、芬太尼和丁丙诺啡。尽管使用了较短的萃取/解吸时间（5 分钟/5 秒），但在使用 300 μL 样品量对所有分析物进行评估的范围内，仍以良好的准确度 (>= 90%) 和线性 (R-2 > 0.99) 获得了低于世界反兴奋剂机构 (WADA) 设定的最低要求性能水平 (MRPL) 的定量限。在线技术，例如多级裂解 (MRM3) 和微分淌度的多反应监测使用光谱测定法 (DMS) 来增强该方法的选择性，同时又不影响分析速度。根据计算，一旦与高通量相结合，基于 96 孔板格式，该方法的每个样品的制备时间可能低至 15 秒。我们的结果表明，Bio-SPME-OPP-MS 有效地集成了采样/样品净化和大气压电离，使其成为多种生物分析应用的有利配置，包括运动兴奋剂、体内组织采样和治疗药物监测。
In recent years, the direct coupling of solid phase microextraction (SPME) and mass spectrometry (MS) has shown its great potential to improve limits of quantitation, accelerate analysis throughput, and diminish potential matrix effects when compared to direct injection to MS. In this study, we introduce the open port probe (OPP) as a robust interface to couple biocompatible SPME (Bio-SPME) fibers to MS systems for direct electrospray ionization. The presented design consisted of minimal alterations to the front-end of the instrument and provided better sensitivity, simplicity, speed, wider compound coverage, and high-throughput in comparison to the LC-MS based approach. Quantitative determination of clenbuterol, fentanyl, and buprenorphine was successfully achieved in human urine. Despite the use of short extraction/desorption times (5 min/5 s), limits of quantitation below the minimum required performance levels (MRPL) set by the world antidoping agency (WADA) were obtained with good accuracy (>= 90%) and linearity (R-2 > 0.99) over the range evaluated for all analytes using sample volumes of 300 mu L. In-line technologies such as multiple reaction monitoring with multistage fragmentation (MRM3) and differential mobility spectrometry (DMS) were used to enhance the selectivity of the method without compromising analysis speed. On the basis of calculations, once coupled to high throughput, this method can potentially yield preparation times as low as 15 s per sample based on the 96-well plate format. Our results demonstrated that Bio-SPME-OPP-MS efficiently integrates sampling/sample cleanup and atmospheric pressure ionization, making it an advantageous configuration for several bioanalytical applications, including doping in sports, in vivo tissue sampling, and therapeutic drug monitoring.