Recent advances in nanostructure/nanomaterial-assisted laser desorption/ionization mass spectrometry of low molecular mass compounds.

Laser desorption ionization mass spectrometry (LDI-MS) has been developed to be an essential tool for the analysis and identification of a large variety of species, ranging from small metabolites, drugs and pollutants to peptides and proteins and even to bacteria. Matrix assisted LDI-MS has shown a great power for macromolecules, but its analytical capability to low mass compounds is limited due to inherent drawbacks, including abundant interference in low mass range (<800 Da) caused by matrix self-dissociation and poor reproducibility due to inhomogeneous crystallization. Several matrix-free methods have been developed to solve these issues, mainly through altering organic matrix with inorganic nanostructured surfaces or nanomaterials as LDI medium. In the past five years, improvements on conventional silicon-based, metal-based, metal oxide-based and carbon-based LDI media as well as emerging novel materials such as 2D nanomaterials and organic frameworks have gained important progresses. Meanwhile, with the deep research in light-matter interaction, LDI mechanism studies begin to grow and become to attach great importance. Advances in both medium and mechanism promote to expand the applicable potential of nanostructure/nanomaterial-assisted LDI-MS in many aspects, including trace analysis, structural analysis and MS imaging. In this review, we survey the major progresses in this area in recent years. We also sketch remaining challenges and directions for future development.