Enriching analyte molecules on tips of superhydrophobic gold nanocones for trace detection with SALDI-MS

The sensitivity of surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) analysis depends on the efficiency of desorption and ionization of analyte molecules, which is usually limited by the low utilization efficiency of laser energy. Herein we demonstrate an efficient method to increase energy utilization efficiency for improving the efficiency of desorption and ionization of analyte molecules in SALDI-MS analysis. To increase the utilization efficiency of energy, a superhydrophobic gold film covered silicon nanocone array is fabricated and used as SALDI substrate. The nanocone array increases the absorption up to 99.65% at the wavelength of 355 nm, which is applied for SALDI-MS detection. The superhydrophobicity promotes the analyte molecules concentrated on the tips of nanocones where photon energy is confined, therefore, more energy can be provided for desorption and ionization of analytes. The energy efficiency is increased by using this substrate. The sensitivity of SALDI-MS analysis is greatly improved. For example, 100 amol/μL of rhodamine 6G, 100 fmol/μL of polyethyleneglycol, 100 ymol/μL of glutathione and 100 ymol/μL arginine still can be analyzed. The lake water containing malachite green was used as the real sample. The regression equation (Log I = 0.39 Log C + 6.58, R² = 0.9811) was obtained when the concentration of analyte was in the range from 10^-4 mol/L to 10^-8 mol/L. Therefore, the calculated LOD and LOQ are 1.35 × 10^-14 mol/L and 1.35 × 10^-7 mol/L, respectively. In addition, the lower relative standard deviation (0.7%, n = 10), proper recovery (113% and 91%), and low matrix effect (-1.1% and -1.1%) all demonstrate the great potential of the designed substrate in practical analysis.