Analysis of polyisoprene oligomers via in situ silver nanoparticle formation on thin-layer chromatography plate using matrix-assisted laser-induced desorption/ionization mass spectrometry

The direct mass spectrometry (MS) detection of polyisoprene (PI) oligomers on a thin-layer chromatography (TLC) plate using matrix-assisted laser-induced desorption/ionization (MALDI) with silver trifluoroacetate as the cationization reagent was investigated. The spots of PI oligomers and silver trifluoroacetate on the TLC plate resulted in brown materials after UV laser irradiation. It was suggested that silver trifluoroacetate yielded Ag nanoparticles as brown materials after heating via laser irradiation. The nanoparticles behaved as an inorganic matrix and a source of Ag+ adduct in the analysis of PI oligomers. The use of organic matrices together with silver trifluoroacetate reduced the signal intensity of PI oligomers on MALDI-MS on a TLC plate. The separation of PI oligomers (polymerization degree, n = 5–11) by TLC resulted in a single elliptical spot without a clear separation after the chromatographic procedure. However, in MS imaging, differences in migration lengths based on degrees of polymerization were clearly observed and the degrees of polymerization were identified without comparison with standards.