Comparison of sample pre-treatments for laser desorption ionization and secondary ion mass spectrometry imaging of Miscanthus x giganteus.

Efforts to further the potential of the large perennial grass Miscanthusxgiganteus as a biofuel feedstock would be aided by the ability to image the chemical species present during the fuel production process. Toward this end, two mass spectrometry imaging (MSI) approaches have been investigated here-laser desorption/ionization mass spectrometry (LDI-MS) and secondary ion mass spectrometry (SIMS). As a first step, cross sections of Miscanthus were subjected to a variety of sample preparation methods to optimize conditions for MSI. For LDI-MS, a thin metal coating (2 nm thick Au) provided high quality signals of saccharide-related ions. The traditional matrix-assisted laser desorption/ionization matrix, 2,5-dihydroxybenzoic acid, also showed high efficiency for the desorption of saccharide-related ions. In contrast, with alpha-cyano-4-hydroxycinnamic acid matrix, these ions were nearly absent in the mass spectra. Direct laser ablation of untreated Miscanthus sections was also performed. High resolution images, where the fine structure of the vascular bundle could be clearly visualized, were obtained using SIMS. Although coating the sections with a nanometer thick Au layer can greatly enhance the quality of SIMS images, the coating had limited effect on secondary ion signal enhancement. Using the optimized mass spectrometry approaches described here, information on the spatial distribution of several saccharides was obtained.