Investigating the position of the separation capillary and emitter tube tips in a nanoflow sheath-liquid CE-ESI-MS interface to decouple the ESI potential.

Robust decoupling of the ESI potential from the separation potential in CE-ESI-MS interfaces is very important for the high performance of the CE-ESI-MS devices and their applications for highly sensitive analyses of ionogenic compounds. In this study, we utilize a nanoflow sheath-liquid CE-ESI-MS interface composed of a quartz emitter and a separation fused silica capillary treated by etching, which are threaded to cross coupling for sheath liquid and electrode connection. Specifically, we have tested the ability of the interface to decouple the ESI potential from the separation potential at different positions of the separation capillary and ESI emitter tube tips. The interface with the separation capillary tip protruding the emitter tip by 20 μm did not provide sufficient robustness. The real ESI potential (delivered as 2.0 kV from the independent high voltage power supply HV2) ranged from 2.1 kV to 4.5 kV depending on the applied separation voltage (12.0-20.0 kV, provided by the power supply HV1) and electric conductivity of the background electrolyte (BGE) used. The interface robustness was partially improved when the capillary tip was aligned with the emitter tip. However, the complete decoupling of the spray and separation potentials was achieved only when the capillary tip was retracted 20 μm inside the emitter. In this arrangement, the ESI potential was stable and independent of both the separation potential (voltage) and the BGE conductivity. Moreover, this setting provided better sensitivity for the CE-ESI-MS analysis of selected drugs and benzylpyridinium cations than the setup with the capillary tip aligned with or protruding the emitter tip.