Initial experiments on infrared matrix-assisted laser desorption/ioniz
ation mass spectrometry (IR-MALDI) using a free electron laser in the
analysis of low-molecular-weight compounds are reported. Mass spectra
from samples of ethylenediaminetetraacetic acid (EDTA), nitrilotriacet
ic acid (NTA) and a phosphate salt were obtained. Low molecular weight
(LMW) compounds are of similar mass as the molecular weight of the ma
trix compound and interference between matrix and analyte ions can deg
rade MALDI sensitivity. Under optimal conditions, however, we find lit
tle interference and that often the analyte signal exceeds the matrix
signal, a result also observed in UV-MALDI of these compounds, In the
IR-MALDI of EDTA near 3.0 mu m the FEL results are similar to those ob
tained using a fixed frequency 2.94 mu m Er:YAG laser of 200 ns pulse
duration. However. the tunable FEL laser can selectively excite partic
ular vibrational modes of the matrix (e.g., an OH or CO stretch) or of
residual water contained within the crystalline MALDI sample. This ca
pability was used to explore possible vaporization and ionization mech
anisms of IR-MALDI for EDTA. (C) 1998 Pacific Northwest National Labor
atory. Published by Elsevier Science B.V.