Dopant-assisted atmospheric pressure photoionization Orbitrap mass spectrometry - An approach to molecular characterization of lignin oligomers.

Lignin is the second most abundant biopolymer in nature and is considered an important renewable source of aromatic compounds. One of the most promising analytical methods for molecular characterization of lignin is Orbitrap high-resolution mass spectrometry with atmospheric pressure photoionization (APPI), proved itself in the study of lignins of various origins and their depolymerization products. In this work, the photoionization of lignin using acetone, 1,4-dioxane, and THF as solvents for the biopolymer and APPI dopants providing the generation of protonated and deprotonated molecules of lignin oligomers has been studied. The ionization conditions were optimized on the basis of the dependences of the total ion current on temperature and the flow rate of the solution into the ion source. Lignin degradation processes under APPI conditions occur mainly with the cleavage of ether ß-O-4 bonds between phenylpropane structural units, demethylation (negative ion mode), as well as the loss of water and formaldehyde (positive ion mode). Negative ion mode APPI provides a higher ionization efficiency in the region of high molecular weights, however, it is characterized by an increased fragmentation of ß-O-4 ether bonds compared to APPI(+) leading to a partial depolymerization of lignin in the ion source. The combination of APPI with Orbitrap high-resolution mass spectrometry allows obtaining mass spectra of coniferous and deciduous wood lignins with resolved fine structure and containing signals of up to 3000 oligomers in the mass range of 300-1800 Da. This can be used for comprehensive characterization of lignins at molecular level and tracking changes in biopolymer chemical composition in various processes.