Structural Characterization of Acidic Compounds in Pyrolysis Liquids Using Collision-Induced Dissociation and Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

In this study, a novel approach to characterize and identify acidic oil compounds utilizing the fragmentational behavior of their corresponding precursor ions is presented. Precursor ions of seven analyzed pyrolysis oils that were generated from pyrolysis educts of different origins and degrees of coalification were produced by electrospray ionization in the negative ion mode (ESI(-)). Following a fragmentation of all ions in the ion cloud by collision-induced dissociation (CID), the precursor and product ions were subsequently detected by ultrahigh resolving Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). The ESI(-)-CID data sets were evaluated by applying either a targeted classification or untargeted clustering approach. In the case of the targeted classification, 10% of the ionized precursor ions of the analyzed pyrolysis liquid samples could be classified into one of 11 compound classes utilizing theoretical fragmentation pathways of these classes. In contrast, theoretical fragmentation pathways were not necessary for the untargeted clustering approach, making it the more transmittable method. Results from both approaches were verified by analyzing standard compounds of known structure. The analysis and data evaluation methods presented in this work can be used to characterize complex organic mixtures, such as pyrolysis oils, and their compounds in-depth on a structural level.