Electrophoretic separation-mass spectrometric detection on polymer microchip directly integrated with a nanospray tip

We fabricated a polymer chip for microchip electrophoresis-mass spectrometry (MCE-MS). As a substrate material, cycloolefin polymer (COP) was selected due to its high chemical durability and easy metallization for the electrode. A COP microchip with a conventional cross-type channel configuration for the MCE separation was fabricated by hot embossing. After bonding with a rid substrate, a nano electrospray ionization (nano-ESI) tip structure for MS detection was machined directly at the opening of the separation channel end. A gold electrode to keep the electric contact for ESI was deposited around the nanospray tip by electron beam evaporation. When the voltage of 3.0 and 2.0 kV was applied to the inlet and the ESI electrode, respectively, the formation of Taylor cone and stable electrospray were observed at the channel opening. In infusion analysis of caffeine, the MS spectrum with parent mass number of 195, which accords with that of the protonated caffeine, was successfully obtained in the positive mode. Furthermore, the MCE separation and ESI-MS detection of caffeine and arginine was also successfully achieved with resolution of 1.0. Therefore, these results demonstrated that the fabricated microchip integrated with the nano-ESI tip can be employed as the MCE-ESI-MS device.