Paper-spray Ionization-Mass Spectrometry for Chemical Monitoring of Organic Reactions and Extracellular Microenvironments (#13)
Applications of droplets for studies in small culture volume, especially microdroplets in microfluidics, have aroused increasing interests from physical, chemical and biological fields.1 The identification and quantitation of the matters in microdroplets were mainly accomplished by optical methods, which require chromophoric substrates or labeling. Since mass spectrometry (MS) is a universal label-free, sensitive, and molecularly specific method, the integration of MS into the online analysis of droplets is apparently of great importance. In this work, droplets with controllable volume and time interval in the ranging from 20 nL to 2.4 μL and 1.5 s to 60 s respectively were sequentially generated at a capillary outlet. Induced by electrostatic attraction, droplets were split from the solution and attracted to a paper.Paper-spray ionization is a highly promising atmospheric pressure electrospray-based ionization (ESI) technique inconsideration of its simplified protocol of sample preparation and equipment.23 Combining the droplets with online MS via paper-spray ionization, a steady flow of solvent was delivered to the base-side of the paper, which maintained the consistent state of paper-spray.4 Each droplet engendered an individual peak in the ion chromatogram with relative standard deviations (RSDs) not higher than 9% for both the intensities and the time intervals. As a proof-of-principle, the present method was utilized for the monitoring of the amine-aldehyde condensation reaction of butylamine and benzaldehyde. Furthermore, an online and real-time MS sensor for chemical monitoring of extracellular microenvironments was established by the integration of a microdialysis module. Glucose concentration in the culture medium of HepG2 cells was monitored, and the effects of some drugs were investigated. We believe this method would play a more important role through future combinations with microfluidic devices.56
This work was supported by National Natural Science Foundation of China (Nos. 21227006, 21275088).
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