Matrix‐assisted laser desorption ionization (MALDI) mass spectrometry has found considerable acceptance by the analytical community. Though the principal ideas are well‐established, i.e. the incorporation of analyte molecules into a solid matrix (usually solid), the resonant excitation of the matrix molecules by an intense short pulse of laser light (either UV or IR) inducing a phase transition of a microvolume and desorbing intact matrix and analyte molecules, and the charging of analytes by (photo)chemical ionization processes, understanding of the underlying elementary processes is still rudimentary and optimization of the experimental parameters is done empirically. The current status of the analytical applications will be described. Whereas molecular weight determination of proteins is routinely done in many laboratories today, the technique can also be applied to other classes of biomolecules, such as glycoconjugates, carbohydrates and nucleic acids, as well as to technical polymers. The current understanding of the desorption ionization process is discussed, emphasizing the authors investigations of the incorporation and ablation phenomena.

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