Microfabricated Dual Sprayer for On-Line Mass Tagging of Phosphopeptides

Phosphopeptides tagging reactions by dinuclear zinc(II) complexes (1,3-bis[bis(2-pyridylmethyl)amino]-propan- 2-olato dizinc(II)3+, called tag) were performed with a dual-channel microsprayer in electrospray ionization mass spectrometry. The reaction is first studied ex situ and analyzed with a commercial electrospray source. In situ reactions (i.e., inside the Taylor cone) were achieved with a dual-channel microsprayer both with the tag synthesized chemically before the experiments and with the tag electrogenerated by in situ oxidation of a zinc electrode, also used to apply the electrospray current. The device consists of a polyimide microchip with two microchannels $(20 \mu m \times 50 \mu m \times 1 cm)$ etched on each side of the structure and connecting only at the tip of the microchip. We demonstrate here that mixing two solutions with different physicochemical properties inside the Taylor cone can be used to selectively tag target molecules.