Plasmonic nanoshells enhanced laser desorption/ionization mass spectrometry for detection of serum metabolites

•The enhancement mechanism of laser desorption/ionization process is revealed by plasmonic particles with hot carriers.•Superior analytical sensitivity and selectivity are achieved for detection of small metabolites over conventional matrices.•The real case application of plasmonic particles is demonstrated in detection of serum samples towards clinical use.

Laser desorption/ionization mass spectrometry (LDI MS)-based small metabolites detection is fundamentally important for the clinic prognoses and diagnoses. Plasmonic materials have been applied as efficient substrates for LDI MS of these molecules. However, there is no clear understanding of the mechanism of using plasmonic materials for enhanced LDI MS of small metabolites, thus restricting their application for real case serum samples. In this work, we report the use of plasmonic nanoshells for enhanced LDI MS detection of small analytes. The antibonding modes of Au nanoshells provided unique opportunity for the generation of hot carriers in the ultra-violet (UV) optical range. This effect of the Au nanoshells displayed desirable analytical sensitivity and endurance towards small metabolites (e.g. amino acids) in complex protein/mixtures as compared to Au nanorods/nanospheres and conventional organic matrix. Further we achieved LDI MS profiling and detection of small metabolites from complex serum samples by Au nanoshells. Our work not only shed light on the enhancement mechanism of LDI MS detection using plasmonic nanoparticles with hot carriers, but also contributed to the real case application of LDI MS in clinical study.

Graphical abstractLaser desorption/ionization mass spectrometry analysis of serum metabolites based on plasmonic Au nanoshells.Download high-res image (155KB)Download full-size image