The water loss process in Laser Mass Spectrometry of amine terminal amino acids was studied. Water loss is proposed to occur via a thermal decomposition mechanism for a protonated amino acid forming a protonated lactam ring. The magnitude of the water loss peak is correlated with the stability of the protonated lactam ring. Semi-empirical MNDO calculations of the heat of reaction of a protonated amino acid forming a protonated lactam ring and water support the correlation. The substrate (matrix) appears to have little effect on the process; results are essentially the same with the use of different substrates and sample preparation methods.

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