A method of collecting and sensing a biofluid with enhanced concentration of analytes due to electroporation comprises electroporating biofluid glands (14) that are generating a biofluid and specifically sensing at least one analyte in said biofluid, the at least one analyte having a molecular weight greater than 50 Da. A device (100) wearable on a user's skin (12) for receiving an advective flow of a biofluid comprises at least one of a biofluid stimulation component (140), a biofluid sensor (220, 222) specific to an analyte, or a biofluid collection element (230, 232), at least one electroporation electrode (290) for enhancing concentration of at least one analyte in the biofluid having a molecular weight of greater than 50 Da, a counter electrode (195), and an electroporation waveform generator configured to cause the electroporation electrode (290) to generate and direct a plurality of electroporation pulses into the skin (12).
