Chapter 17: Inlet and Vacuum Ionization from Ambient Conditions

The discovery that laser ablation of a common MALDI matrix at atmospheric pressure without use of a voltage produced ions with nearly identical charge states to ESI led to a series of new ionization methods that we have given the general term inlet and vacuum ionization. The initial thought that the laser was necessary for matrix-assisted ionization gave way to ionization requiring a heated inlet with a pressure-drop region and then to a matrix that could be a solvent or no matrix. This in turn led to laser ablation in vacuum producing multiply charged ions without an inlet, and finally to the present where we have found matrices that lift molecules into the gas phase as ions without any external energy source. Our mechanistic view of this new ionization process developed into ionization methods for use in mass spectrometry will be discussed. These methods are simple to use, safe, robust, and sensitive. Several approaches for high-throughput analyses of compounds irrespective of their molecular weight will be presented using low- and high-performance mass spectrometers.