Online monitoring of chemical reactions by polarization-induced electrospray ionization

• PI-ESI MS is used to carry out fast reactions and ionization simultaneously.
• Reaction species (∼10 μL) can be on-line monitored using PI-ESI MS in real time.
• Intermediates can be detected by PI-ESI MS within 100 ms.
• Selective detection and quantification of acetone in urine samples by PI-ESI MS are demonstrated.

Polarization-induced electrospray ionization (PI-ESI) is a simple technique for instant generation of gas-phase ions directly from a microliter-sized droplet for mass spectrometric analysis. A sample droplet was placed over a dielectric substrate and in proximity (2–3 mm) to the inlet of a mass spectrometer. Owing to the polarization effect induced by the high electric field provided by the mass spectrometer, the droplet was polarized and the electrospray was generated from the apex of the droplet. The polarization-induced electrospray could last for tens of seconds, which was sufficiently long to monitor fast reactions occurring within few seconds. Thus, we demonstrated the feasibility of using the droplet-based PI-ESI MS for the online monitoring of fast reactions by simply mixing two droplets (5–10 μL) containing reactants on a dielectric substrate placed in front of a mass spectrometer applied with a high voltage (−4500 V). Schiff base reactions and oxidation reactions that can generate intermediates/products within a few seconds were selected as the model reactions. The ionic reaction species generated from intermediates and products can be simultaneously monitored by PI-ESI MS in real time. We also used this approach to selectively detect acetone from a urine sample, in which acetone was derivatized in situ. In addition, the possibility of using this approach for quantitative analysis of acetone from urine samples was examined.

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