Analytical Aspects of Atmospheric Pressure Ionisation in Mass Spectrometry

The actual signal recorded with an analytical instrument is not always a true reflection of the analysed sample. In this thesis a further insight of the atmospheric pressure ionisation processes electrospray (ESI) and atmospheric pressure chemical ionisation (APCI) has been endeavoured, to provide a deeper understanding of and ways to minimize this bias. A response model for ESI has been modified and used to study the influence of solvent composition on the observed mass spectrometric signal. The response model divides the response into an analyte partitioning coefficient and an instrumental response factor. A number of experimental parameters influencing the response were investigated including spray position relative to the orifice, spray potential, nebulizer and curtain gas flow rates, ionic strength and organic content of the sprayed solution. The history of the generated droplets turned out to be of significant importance to both the partitioning coefficients and the instrumental response factor. Furthermore, it was found that the total ionic strength and not only the electrolyte concentration will influence the instrumental response factor. In addition, based on the importance of hydrophobicity and electrophoretic mobility, a model was proposed for the ion distribution within the electrosprayed droplets. The coupling of an electrochemical (EC) cell to a mass spectrometric (MS) system has been evaluated. The coupling of the EC cell to the MS was made to decouple the cell from the high voltage circuit of the ESI. The feasibility for analyte ionisation, sample pre-concentration and solvent exchange as well as studying redox reaction products was shown