RESUMEN
The electrospray ionization of highly conductive solutions containing Triton X-100, a nonionic surfactant, is found to induce alternating periods of surfactant enrichment and depletion when the concentration of the surfactant is near the critical micelle concentration (CMC) and when the flow rate is on the order of 10 nL/min. Analyzing the surfactant-protein mixture shows that the protein is partially denatured during the surfactant enrichment. The measurement of the phospholipid and oligosaccharide mixture prepared in the surfactant solution shows that the ion signal of the lipid is in phase with, and the hydrophilic oligosaccharide is out of phase with the surfactant signal. The results suggest that this novel phenomenon can be exploited for in situ separation of compounds in ESI-MS. Besides the ion signal, the condition of the alternating phase is also reflected in the spray current and Taylor cone's apex angle. The phase separation is likely related to the formation of a micelle in the Taylor cone and can be selectively triggered by tuning the flow rate with emitter voltage for an on-demand application.
RESUMEN
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.
RESUMEN
Oxidative modification is usually used in mass spectrometry (MS) for labeling and structural analysis. Here we report a highly tunable oxidation that can be performed in line with the nanoESI-MS analysis at the same ESI emitter without the use of oxidative reagents such as ozone and H2O2, and UV activation. The method is based on the high-pressure nanoESI of a highly conductive (conductivity >3.8 S m-1) aqueous solution near the minimum flow rate. The ion source is operated under super-atmospheric pressure (0.5 MPa gauge pressure) to avoid the contribution of electric discharge. The analyte at the tip of the Taylor cone or in the emitter droplet can be locally oxidized in an on-demand manner by varying the nanoflow rate. With an offline nanoESI, the degree of oxidation, i.e., the average number of incorporated oxygen atoms, can be finely tuned by voltage modulation using spray current as the feedback signal. Oxidations of easily oxidized residues present in peptides/proteins and the double bonds of the unsaturated phosphatidylcholine occur at low flow rate operation (<5 nL min-1) when the electric field at the tip of the Taylor cone and the initially produced charged droplet reaches approximately 1.3 V nm-1. The oxidized ion signal responds instantaneously to changes in flow rate, indicating that the oxidation is highly localized. Using isotope labeling, it was found that the incorporated oxygen primarily originates from the gas phase, suggesting a direct oxidation pathway for the analyte enriched on the liquid surface via the reactive oxygen atoms formed by the strong electric field.
RESUMEN
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.