A simple nanoelectrospray arrangement with controllable flowrate for mass analysis of submicroliter protein samples

A simple arrangement for nanoelectrospray ionization using a conventional syringe pump connected to a pulled unmodified capillary has been evaluated. This arrangement avoids several disadvantages associated with metal-coated nanoelectrospray emitters. The relatively large orifice (approximately 9 microns) at the pulled capillary tip reduces sample clogging and the use of the pump minimizes spray disruption due to gas bubbles. Subattomole detection limit was achieved with nanomolar protein sample solutions at 5-10 nL/min flowrates using an LCQ mass spectrometer. Submicroliter samples can be loaded from the tip orifice and stored inside the capillary to virtually eliminate any dead volume, and then be electrosprayed for extended periods at well-controlled flowrates.