Ionic liquid matrices for MALDI mass spectrometry of lignin

The use of matrix-assisted laser desorption/ionization (MALDI) mass spectrometry for the study of lignin is still extremely limited due to its low ionization efficiency. We have developed an approach for obtaining high-intensity MALDI mass spectra of lignin, based on the use of ionic liquids as matrices. Thirty-two ionic liquids consisting of large nitrogen-containing cations and anions of aromatic acids, traditionally used as crystalline matrices, were tested. It was established that ionic liquids based on N,N-diisopropyl-N-ethylammonium, N-isopropyl-N-methyl-N-tert-butylammonium, 3-aminoquinolinium, pyridinium, and 1-methylimidazolium cations and anions of ferulic, α-cyanohydroxycinnamic, and 2,5-dihydroxybenzoic acids as MALDI matrices provided high efficiency of lignin desorption/ionization with generation of singly charged protonated molecules of its oligomers. The use of such matrices in combination with the MALDI quadrupole ion trap–time-of-flight technique allows high-intensity mass spectra of lignin to be obtained without interferences from the matrix in the molecular weight range up to 3 kDa, adequately reflecting the molecular mass characteristics of lignin preparations. Using ionic liquid matrices, MS2 and MS3 MALDI mass spectra of lignins for various precursor ions were first obtained, including in the region of large (> 2 kDa) molecular weights. Differences in tandem mass spectra of coniferous and deciduous lignins, reflecting the structural features of corresponding oligomers were demonstrated.