Influence of surface melting effects and availability of reagent ions on LDI-MS efficiency after UV laser irradiation of Pd nanostructures

In this study, the influence of surface morphology, reagent ions and surface restructuring effects on atmospheric pressure laser desorption/ionization (LDI) for small molecules after laser irradiation of palladium self-assembled nanoparticular (Pd-NP) structures has been systematically studied. The dominant role of surface morphology during the LDI process, which was previously shown for silicon-based substrates, has not been investigated for metal-based substrates before. In our experiments, we demonstrated that both the presence of reagent ions and surface reorganization effects – in particular, melting – during laser irradiation was required for LDI activity of the substrate. The synthesized Pd nanostructures with diameters ranging from 60 to 180 nm started to melt at similar temperatures, viz. 890-898 K. These materials exhibited different LDI efficiencies, however, with Pd-NP materials being the most effective surface in our experiments. Pd nanostructures of diameters >400-800 nm started to melt at higher temperatures, >1000 K, making such targets more resistant to laser irradiation, with subsequent loss of LDI activity. Our data demonstrated that both melting of the surface structures and the presence of reagent ions were essential for efficient LDI of the investigated low molecular weight compounds. This dependence of LDI on melting points was exploited further to improve the performance of Pd-NP-based sampling targets. For example, adding sodium hypophosphite as reducing agent to Pd electrolyte solutions during synthesis lowered the melting points of the Pd-NP materials and subsequently gave reduced laser fluence requirements for LDI.