Use of Nanoparticle Decorated Surface-Enhanced Raman Scattering Active Sol–Gel Substrates for SALDI-MS Analysis

Spectroscopy and mass spectrometry techniques are sometimes combined into the same analytical workflow to leverage each technique’s analytical benefits. This combined workflow is especially useful in forensic and medical contexts where samples are often precious in nature. Here, we adopt metal nanoparticle (NP) doped sol–gel substrates, initially developed for surface-enhanced Raman scattering (SERS) analysis, as surface-assisted laser desorption/ionization–mass spectrometry (SALDI-MS) substrates. Using dried blood and sample protocols previously developed for SERS analysis, we observe heme-related spectral features on both silver and gold NP substrates by SALDI-MS, demonstrating dual functionality for these orthogonal techniques. Modifying the dried blood extraction procedures also allows for the observation of blood triacylglycerols by SALDI-MS. This is the first demonstration of a SERS/SALDI-MS substrate based on a sol–gel scaffold and the first demonstration of a gold NP sol–gel substrate for SALDI-MS which features lower substrate-related SALDI-MS background compared to the silver substrate.