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In accordance with the purpose (s) of the present disclosure, as embodied and broadly described herein, the disclosure, in one aspect, relates to a vibrating sharp edge spray ionization (VSSI) method suitable for coupling with a mass spectrometer, a VSSI method modified with a capillary suitable for use with continuous-flow separation methods such as liquid chromatography, and a VSSI method suitable for coupling with a capillary electrophoresis (CE) device in order to introduce the CE sample flow into a mass spectrometer. Also disclosed herein are devices for carrying out these methods and methods of making the same. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure.