Functionalization of silicon nanowire arrays by silver nanoparticles for the laser desorption ionization mass spectrometry analysis of vegetable oils

In this work, novel hybrid nanostructured surfaces, consisting of dense arrays of silicon nanowires (SiNWs) functionalized by Ag nanoparticles (AgNP/SiNWs), were used for the laser desorption/ionization time-of-flight mass spectrometry (LDI-TOF MS) analysis of some typical unsaturated food components (e.g. squalene, oleic acid) to assess their MS performance. The synthesis of the novel platforms is an easy, cost-effective process based on the maskless wet-etching preparation at room temperature of SiNWs followed by their decoration with AgNPs, produced by pulsed laser deposition. No particular surface pretreatment or addition of organic matrixes/ionizers was necessary. Moreover, oil extracts (e.g. extra virgin olive oil, peanut oil) could be investigated on AgNP/SiNWs surfaces, revealing their different MS profiles. It was shown that such substrates operate at reduced laser energy, typically generating intense silver cluster ions and analyte adducts. A comparison with bare SiNWs was also performed, indicating the importance of AgNP density on NW surface. In this case, desorption/ionization on silicon was invoked as probable LDI mechanism. Finally, the influence of SiNW length and surface composition on MS results was assessed. The combination of typical properties of SiNWs (hydrophobicity, antireflectivity) with ionization ability of metal NPs can be a valid methodology for the further development of nanostructured surfaces in LDI-TOF MS applications.