A setup for the coupling of a thin-layer electrochemical flow cell to electrospray mass spectrometry

A novel setup for the coupling of a commercially available thin-layer cell to electrospray mass spectrometry (ESI-MS) which allows the electrochemical reactions at the counter electrode to be straightforwardly separated from the flow into the mass spectrometer has been developed. In this way, interferences from reaction products formed at the counter electrode can be minimized. This reduces the risk of changes in the mass spectra as a result of electrochemical reactions in the solution. The described setup also enables the working electrode to be positioned close to the electrospray (ESI) emitter without the need for a grounding point or a long transfer line between the electrochemical cell and the electrospray emitter. By decoupling the electrochemical reactions in the flow cell and those in the electrospray emitter, improved facilities for studies of electrochemical reactions are obtained through a better control of the potential of the working electrode. The setup has been used to study the oxidation of a drug (Olsalazine), which previously has been found to involve chemical follow-up reactions. It is also demonstrated that uncharged thiols can be detected in ESI-MS after spontaneous adsorption on a gold working electrode, followed by oxidative desorption to yield sulfinates or sulfonates. This adsorption and potential-controlled desorption has been used for the preconcentration of micromolar concentrations of 1-hexanethiol as well as for desalting of solutions containing micromolar concentrations of thiols. The results indicate that the present on-line coupling of an electrochemical cell to ESI-MS provides promising possibilities for sample preconcentration, matrix exchange (including desalting), and ionization of neutral compounds, such as thiols.     

A method for determination of ion distribution within electrosprayed droplets

A simplified method for determination of ion distribution within electrospray ionization droplets has been developed. The method is based on an electrospray ionization mass spectrometry equilibrium partitioning model recently developed by Enke (Enke, C. G. Anal. Chem. 1997, 69, 4885-4893). This "simple" method required only two samples to be analyzed at each solution composition compared to the method previously reported. Furthermore, as the same m/z value is monitored in both experiments, possible effects of the mass-dependent ion transmission in the quadrupole were eliminated. Tetra-alkylammonium compounds with variable hydrophobicity were used as model compounds and the effect of methanol-water composition in the electrosprayed solution was studied. It was found, as expected, that the signal optimized at a high content of methanol in the electrosprayed solution. The distribution coefficient for analyte ions between the droplet surface and bulk solution maximize, however, at a lower content of methanol in the electrosprayed solution.