Application and Evaluation of Solvent-Free Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry for the Analysis of Derivatized Fullerenes

Abstract

A variety of derivatized fullerenes have been studied by matrix-assisted laser desorption/ionization (MALDI) mass spectrometry. Of particular emphasis has been the evaluation of a recently introduced solvent-free sample/target preparation method. Solvent-free MALDI is particularly valuable in overcoming adverse solvent-related effects, such as insolubility and/or degradation of the sample. The method was applied to fullerene derivatives susceptible to decomposition under insufficiently “soft” MALDI conditions. Analytes included the hydrofullerene: C60H36, fluorofullerenes: C60F x where x = 18, 36, 46, 48 and C70F x where x = 54, 56, methano-bridged amphiphilic ligand adducts to C60 and the [4 + 2] cycloadduct of tetracene to C60. The new solvent-free sample preparation is established as an exceedingly valuable addition to the repertoire of preparation protocols within MALDI. The MALDI mass spectra were of very high quality throughout, providing a testimony that “soft” MALDI conditions could be achieved. Using the [4 + 2] cycloadduct of tetracene to C60 as the model analyte for direct comparison with solvent-based MALDI, the solvent-free approach led to less fragmentation and more abundant analyte ions. Applying solvent-free sample preparation, different matrix compounds have been examined for use in the MALDI of derivatized fullerenes, including sulfur, tetracyanoquinodimethane (TCNQ), 9-nitroanthracene (9-NA) and trans-2-[3-(4- tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile (DCTB). DCTB was confirmed as the best performing matrix, reducing unwanted decomposition and suppression effects.