Ranganathan Nandhini, Lozier Austin M, Rawson Michael C, Johnson Matthew B, Li Peng
C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, WV, USA.
Department of Physics, West Virginia University, Morgantown, WV, USA.
Rapid Commun Mass Spectrom. 2020 Oct 30;34(20):e8902. doi: 10.1002/rcm.8902.
Direct analysis of chemicals on a surface using mass spectrometry (MS) is of great importance in forensics, food and drug safety, environmental monitoring, and defense. Solvent extraction-based surface analysis offers a convenient way of controlling the desorption conditions and applying internal standards. To date, it mainly relies on a separate electrospray process to nebulize and ionize the solvents. Here, we report a simple and stand-alone ionization system for the solvent extraction-based surface analysis without the need for high voltage, based on vibrating sharp-edge spray ionization (VSSI).
We modified the original VSSI device and developed a stand-alone, integrated surface sampling, and ionization system for MS analysis. By incorporating a micropipette-based solvent dispenser with the VSSI device, the new system performs solvent extraction and ionization, and still maintains a small footprint.
We demonstrated a four order-of-magnitude linear response for glucose spotted on a glass surface with a limit of detection (LOD) of 0.1 pg/mm . We further characterized the performance of this method with a series of compounds and demonstrated a similar LOD to literature values obtained by desorption electrospray ionization. Finally, we applied this method to quantitatively measure the concentration of a pesticide ametryn on spinach surfaces. We demonstrated good linearity (R = 0.99) for ametryn with surface densities in the range of 8-800 pg/mm and an LOD of 9 pg/mm .
We have demonstrated a simple, effective, direct ambient-ionization method that is highly sensitive to molecules on a wide range of surfaces. The flexibility, small footprint, low cost, and voltage-free nature of this method make it an attractive technique for direct surface sample analysis using MS.
使用质谱(MS)直接分析表面化学物质在法医学、食品和药物安全、环境监测及国防领域具有重要意义。基于溶剂萃取的表面分析提供了一种控制解吸条件和应用内标的便捷方法。迄今为止,它主要依赖单独的电喷雾过程来雾化和电离溶剂。在此,我们报道一种基于振动锐边喷雾电离(VSSI)的简单且独立的电离系统,用于基于溶剂萃取的表面分析,无需高压。
我们对原始的VSSI装置进行了改进,开发了一种用于MS分析的独立、集成的表面采样和电离系统。通过将基于微量移液器的溶剂分配器与VSSI装置相结合,新系统实现了溶剂萃取和电离,且仍保持较小的占地面积。
我们证明了在玻璃表面点样的葡萄糖具有四个数量级的线性响应,检测限(LOD)为0.1 pg/mm 。我们用一系列化合物进一步表征了该方法的性能,并证明其LOD与通过解吸电喷雾电离获得的文献值相似。最后,我们将该方法应用于定量测量菠菜表面农药莠灭净的浓度。我们证明了莠灭净在表面密度范围为8 - 800 pg/mm 时具有良好的线性(R = 0.99),LOD为9 pg/mm 。
我们展示了一种简单、有效、直接的常压电离方法,该方法对广泛表面上的分子具有高度敏感性。该方法具有灵活性、占地面积小、成本低以及无需电压的特性,使其成为使用MS进行直接表面样品分析的有吸引力的技术。