C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, WV, USA.
Rapid Commun Mass Spectrom. 2021 Jan;35 Suppl 1(Suppl 1):e8232. doi: 10.1002/rcm.8232. Epub 2018 Aug 19.
The development of miniaturized and field portable mass spectrometers could not succeed without a simple, compact, and robust ionization source. Here we present a voltage-free ionization method, Vibrating Sharp-edge Spray Ionization (VSSI), which can generate a spray of liquid samples using only one standard microscope glass slide to which a piezoelectric transducer is attached. Compared with existing ambient ionization methods, VSSI eliminates the need for a high electric field (~5000 V·cm ) for spray generation, while sharing a similar level of simplicity and flexibility with the simplest direct ionization techniques currently available such as paper spray ionization (PSI) and other solid substrate-based electrospray ionization methods.
The VSSI device was fabricated by attaching a piezoelectric transducer onto a standard glass microscope slide using epoxy glue. Liquid sample was aerosolized by either placing a droplet onto the vibrating edge of the glass slide or touching a wet surface with the glass edge. Mass spectrometric detection was achieved by placing the VSSI device 0.5-1 cm from the inlet of the mass spectrometer (Q-Exactive, ThermoScientific).
VSSI is demonstrated to ionize a diverse array of chemical species, including small organic molecules, carbohydrates, peptides, proteins, and nucleic acids. Preliminary sensitivity experiments show that high-quality mass spectra of acetaminophen can be obtained by consuming 100 femtomoles of the target. The dual spray of VSSI was also demonstrated by performing in-droplet denaturation of ubiquitin. Finally, due to the voltage-free nature and the direct-contact working mode of VSSI, it has been successfully applied for the detection of chemicals directly from human fingertips.
Overall, we report a compact ionization method based on vibrating sharp-edges. The simplicity and voltage-free nature of VSSI make it an attractive option for field portable applications or analyzing biological samples that are sensitive to high voltage or difficult to access by conventional ionization methods.
如果没有简单、紧凑且坚固的离子源,微型化和现场便携式质谱仪的发展将无法成功。在这里,我们提出了一种无需高压(~5000 V·cm)即可产生喷雾的电压自由离子化方法,即振动锐边喷雾离子化(VSSI),它只需要将压电换能器附着在标准显微镜载玻片上即可产生液体样品喷雾。与现有的环境离子化方法相比,VSSI 消除了对喷雾产生所需的高电场的需求,同时与目前可用的最简单的直接离子化技术(如纸喷雾离子化(PSI)和其他基于固体基质的电喷雾离子化方法)具有相似的简单性和灵活性。
通过使用环氧树脂将压电换能器附着在标准玻璃显微镜载玻片上,制造了 VSSI 装置。通过将液滴滴在玻璃载玻片的振动边缘上或用玻璃边缘接触湿表面,将液体样品气溶胶化。通过将 VSSI 装置放置在距质谱仪入口 0.5-1 cm 的位置(Q-Exactive,ThermoScientific)来实现质谱检测。
VSSI 被证明可以离子化包括小分子有机化合物、碳水化合物、肽、蛋白质和核酸在内的各种化学物质。初步的灵敏度实验表明,通过消耗 100 飞摩尔的目标物可以获得高质量的对乙酰氨基酚质谱。还通过在液滴中进行泛素变性来演示 VSSI 的双喷雾。最后,由于 VSSI 的无电压性质和直接接触工作模式,它已成功应用于直接从人指尖检测化学物质。
总体而言,我们报告了一种基于振动锐边的紧凑型离子化方法。VSSI 的简单性和无电压性质使其成为现场便携式应用或分析对高压敏感或难以通过传统离子化方法访问的生物样本的有吸引力的选择。