Investigation of the laser fluence and wavelength dependence in surface‐assisted laser desorption/ionization mass spectrometry using gold nanoparticles

Rationale Surface‐assisted laser desorption/ionization (SALDI) mass spectrometry (MS) builds on the use of nanostructured surfaces (e.g., coatings of colloidal nanoparticles) to promote analyte desorption and ionization. The SALDI process is believed to occur mainly through thermal processes, resulting from heating of the nanosubstrate upon absorption of the photon energy, and by assisting ionization steps. Mostly due to the accessibility of the respective hardware, the majority of SALDI‐MS studies use standard laser wavelengths for MALDI (i.e., 337 or 355 nm), even though peak absorption of the SALDI nanosubstrate might completely differ from these values. Methods Here, we investigated the wavelength dependence in SALDI‐MS to determine if wavelength adjustment would be beneficial, and to provide new experimental data for a better understanding of the SALDI mechanism. To this end, gold nanoparticles (AuNPs) sprayed onto microscope glass slides were employed as SALDI nanosubstrates and L‐arginine as a model analyte. In addition, we used 2,5‐dihydroxyacetophenone (2,5‐DHAP) for classical MALDI‐MS using the same experimental setup. Arginine ion signals were recorded as a function of laser wavelength and laser fluence. Mass spectra were acquired in the wavelength range between 310 and 630 nm, including the absorption maximum of the sprayed AuNPs around 550 nm and that of 2,5‐DHAP around 380 nm. Results Laser fluence thresholds for the generation of arginine ions were found to be dependent on the laser wavelength and to inversely correlate with the absorbance profiles of the deposited AuNPs and 2,5‐DHAP, respectively. Very differently to MALDI, in SALDI ionization efficiency was found to strictly linearly decrease with increasing laser wavelength. Conclusions Our results, therefore, corroborate the general assumption that material ejection in SALDI‐MS is mainly driven by thermal processes in the low laser fluence range and add new evidence that the ionization process is directly influenced by photon energy when AuNPs are employed as nanosubstrates.