Investigations of the Equilibrium Conditions in Plumes of Laser Desorbed Sinapic Acid with Amino Acid Analytes: Influence of Sample Preparation and Matrix to Analyte Ratio

Abstract

The equilibrium nature of a plume of laser desorbed material is examined through the application of a previously developed thermodynamic model to the ion signals observed in 337 nm MALDI mass spectra of mixtures of the matrix sinapic acid with the amino acids alanine, valine, isoleucine, and phenylalanine. Samples are prepared using both conventional dried-droplet and solvent-free methods for comparison. The relative yield of protonated amino acid is shown to increase as the amino acid gas-phase basicity increases for both sample preparation methods. Matrix gas phase basicity values extracted from the equilibrium plots are shown to be in good agreement ([M − H + ] • 876 kJ/mol and [M] 879 kJ/mol) with published experimental values supporting a mechanism wherein the protonated sinapic acid and/or the matrix radical cation act as the proton donor species. These experiments further reveal that there is a large difference in the extracted plume effective temperatures with the solvent-free method yielding lower effective temperatures as compared to the dried-droplet sample preparation, e.g., 552 K versus 1296 K, respectively, at M/A 1:1 (mole/mole). In addition, these experiments suggest that plume effective temperatures decrease as the relative amount of matrix deposited with the analyte increases, regardless of the sample preparation method. Cumulatively, these observations suggest that the crystalline solid allows more efficient transfer of the photoexcitation energy during the sample desorption step, as compared to the solvent-free sample, and/or collisional cooling is more effective for the plume of material desorbed from the solvent-free sample as compared to the conventional dried-droplet sample.