A reconciliation of mass ranges from matrix‐assisted laser desorption/ionization mass spectrometry and size exclusion chromatography for coal‐derived materials

Abstract

AbstractSize exclusion chromatography (SEC) has been used extensively in the characterization of coal‐derived liquids to estimate molecular masses (MM), indicating the presence of considerably greater upper mass ranges compared to mass spectrometric methods based on heated probes and field ionization. In the present study, the use of tetrahydrofuran (THF), a solvent commonly used in SEC, has been shown to lead to partial loss of sample on column packings and to allow some separation by an adsorption mechanism rather than by size exclusion. In this paper, we have compared these results with data from SEC, where 1‐methyl 2‐pyrrolidinone was used as the mobile phase, indicating that the largest molecules (not observed in THF‐based work) appear at the exclusion limit, with a continuum of material down to the total permeation limit of the column. In terms of polystyrene standard masses, this is equivalent to a range from 100 u, at the lower limit, up to in excess of 30–40 000 u and possibly over 2 000 000 u. Our results from SEC in NMP suggest that limitations exist in much solution‐based work attempting to identify distributions of MMs in coal‐derived liquids. Matrix‐assisted laser desorption/ionization (MALDI) spectra of the fractions show similar features to those seen by SEC in NMP, with a continuum from high to low mass, and a significant shift to higher mass in the insoluble fraction compared with the soluble fraction. The new data are in line with observations by laser desorption mass spectrometry (LD‐MS) and MALDI‐MS, which have shown much greater upper‐MM limits than either SEC (in THF) or mass spectrometric techniques relying on thermal evaporation of coal‐derived materials from heated probes. The work would appear to have implications for other polydispersed natural polymer systems.