Wavelength dependence on the level of post-source metastable ion decay observed in infrared matrix-assisted laser desorption ionization

The levels of post-source metastable ion decay (PSD) observed in several peptides and proteins ionized by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI TOF-MS) are measured utilizing both infrared (IR) and ultraviolet (UV) desorption wavelengths. A gridless deceleration ion optic is employed to temporally separate stable analyte ions from analyte metastable neutral and ion fragments. Comparisons of the extent of PSD that is observed in UV-MALDI at 337 nm and IR-MALDI at multiple wavelengths between 2.8 and 3.0 μm are made using the same matrices and analytes. The amount of PSD observed using IR-MALDI was found to be highly dependent on the specific IR wavelength (2.8-3.0 μm) employed for desorption. IR wavelengths shorter than 2.86 μm tended to produce higher levels of PSD, while longer IR wavelengths typically produced significantly less PSD when using a number of common MALDI matrices. Relative PSD levels are quantified by determining the percentage of the neutral fragment signal intensity to the intensity of the stable singly protonated molecular species observed in decelerated MALDI spectra. These studies suggest that an analyte ion activation pathway leading to significant PSD in IR-MALDI may proceed by way of vibrational excitation of the analyte molecules during the desorption event.