Laser desorption/ionization determination of molecular weight distributions of polyaromatic carbonaceous compounds and their aggregates

Molecular weight distributions (MWDs) of model polyaromatic hydrocarbons (PAHs) and complex asphaltene samples have been investigated in laser desorption/ionization mass spectrometry (LDI–MS) experiments. Special efforts are devoted to the characterization of aggregation effects during the desorption process. It is found that non‐covalent clusters of the PAHs and asphaltenes form readily in the desorbing plume. Aggregation is favoured in the experiments performed on dense samples at high laser energy and under continuous ion extraction conditions. In the absence of polar groups in the analyte molecules, the aggregation propensity correlates well with the size of the polycondensed system and with its degree of pericondensation, in qualitative agreement with previous theoretical predictions. For the polydispersed asphaltenes from two different crude oils, MWDs peaking at masses smaller than 500 amu with a high‐mass tail extending up to about 3000 amu have been observed, yielding average weights around 900 amu. Such MWDs are in good agreement with previous mass spectrometric measurement, as well as with diffusion studies in solution. In addition, stable asphaltene aggregates have been detected giving rise to two broad bands in the mass spectrum corresponding to average molecular weights of 2200–3100 amu and 15 000–19 000 amu, respectively. It is concluded that the strong aggregation propensity of asphaltenes is likely to be responsible for the apparent inconsistency between the MWD for these compounds determined by different groups in independent LDI‐MS experiments. The reliability of different sample preparation procedures, including solvent‐free methods, is discussed, and strategies are outlined that serve to apply the potentiality of LDI mass spectrometry to the characterization of covalent and non‐covalent compounds in complex carbonaceous systems. Copyright © 2007 John Wiley & Sons, Ltd.