Rationale: Among isomers of dihydroxybenzoic acid (DHB), 2,5-DHB is often the most efficient matrix in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) for a great variety of compounds. Yet, when performing solvent-free MALDI, 2,6-DHB yields better results for poly(ethylene glycol [PEG]). This intriguing feature is explored here using solid-state nuclear magnetic resonance (NMR).
Methods: Ternary mixtures were prepared by grinding 2,X-DHB (X = 3-6), poly(ethylene glycol) (Mn = 2000 g mol-1 ) and lithium fluoride (LiF) in a matrix/analyte/salt molar ratio of 50/1/10 for 16 min under a controlled atmosphere. After mixing, a few grains were applied to the MALDI target for MS analysis, whereas the major part of the ground sample was transferred into rotors to perform 13 C, 7 Li, and 19 F NMR experiments.
Results: Lithiated PEG chains are mainly formed with 2,6-DHB in solvent-free MALDI, but their abundance increases with 2,3-DHB and 2,4-DHB when water uptake is favored by a humid atmosphere. Solid-state NMR shows that grinding 2,6-DHB-based samples in atmospheric conditions leads to a solid phase in which the matrix, PEG, and salt molecules exhibit a high mobility compared with systems involving other 2,X-DHB isomers. This mobile environment would favor (as a solvent) LiF dissociation and best promote PEG cationization.
Conclusions: Complementary data in 13 C, 7 Li, and 19 F NMR spectra are consistent with the formation of a solid phase of high mobility composed of 2,6-DHB, PEG, and the two salt components that ultimately favor the production of lithiated PEG chains.
© 2020 John Wiley & Sons, Ltd.