ANALYTICAL MASS SPECTROMETRY WITH A SELECTIVE VACUUM ULTRAVIOLET PHOTOIONIZATION SOURCE.

Abstract

The vacuum ultraviolet molecular hydrogen laser is evaluated as a selective ion source for analytical mass spectrometry of easily-ionized compounds. The types of compounds ionized below the photon energy of 7.8 eV include polynuclear aromatic hydrocarbons, and many amines and nitrogen-containing heterocycles. The latter two categories encompass a large number of pharmaceuticals and drugs of abuse. H₂ laser photoionization produces parent molecular ions only, for all compounds studied thus far. Selectivity of the threshold photoionization process is very high, as compounds within as little as 0.2 eV above the threshold are completely rejected. The ability of the technique to discriminate against interfering matrix components is demonstrated for both simple synthetic and complex "real world" mixtures. Easily interpreted spectra are obtained from simple extracts of spiked coffee, beer, soy sauce, urine and blood serum. The most important interference is shown to be electron impact ionization arising from acceleration of stray electrons in the ion source. Most of this ionization is caused by low-energy secondaries generated when stray primaries are collected by the ion source electrodes. The primaries are produced mainly by interaction of scattered laser radiation with metal surfaces. This interference can be controlled through proper instrumental design.