On-demand tunable oxidation is performed during the nanoESI-MS analysis by varying the nanoflow rate and the initial droplet size. The oxidation is initiated when the electric field of the droplet reaches ∼1.3 V nm−1.

A bipolar ESI source is developed to generate a simultaneous emission of charged liquid jets of opposite polarity from an electrodeless sprayer. The sprayer consists of two emitters, and the electrosprays are initiated by applying a high potential difference (HV) across the counter electrodes facing each emitter. The sprayer and the liquid delivery system are made of all insulators without metal components, thus enabling the total elimination of electrochemical reactions taking place at the liquid–electrode interface in the typical electrosprayer. The bipolar electrospray has been implemented using an online configuration that uses a syringe pump for flow rate regulation and an offline configuration that relies on HV for adjusting the flow rate. The voltage–current and flow rate–current relationships of bipolar electrospray were found to be similar to the standard electrospray. The application of bipolar ESI to the mass spectrometry of protein, peptide, and metallocene without electrochemically induced oxidation/reduction is demonstrated.

An electrospray operated in the steady cone-jet mode is highly stable but the operating state can shift to pulsation or multijet modes owing to changes in flow rate, surface tension, and electrostatic variables. Here, a simple feedback control system was developed using the spray current and the apex angle of a Taylor cone to determine the error signal for correcting the emitter voltage. The system was applied to lock the cone-jet mode operation against external perturbations. For a pump-driven electrospray at a regulated flow rate, the apex angle of the Taylor cone decreased with increasing voltage. In contrast, for a voltage-driven electrospray with low flow resistance, the angle was found to increase with the emitter voltage. A simple algorithm based on iterative learning control was formulated and implemented using a personal computer to automatically correct the emitter voltage in response to the error signal. For voltage-driven electrospray ionization (ESI), the feedback control of the spray current can also be used to regulate the flow rate to an arbitrary value or pattern. Electrospray ionization-mass spectrometry (ESI-MS) with feedback control was demonstrated to produce ion signal acquisition with long-term stability that was insusceptible to the emulated external disturbances.