Abstract

Nanomaterials are frequently used in laser desorption ionization mass spectrometry (LDI-MS) as DI enhancers, providing excellent figures of merit for the analysis of low molecular weight organic molecules. In recent years, literature on this topic has benefited from several studies assessing the fundamental aspects of the ion desorption efficiency and the internal energy transfer, in the case of model analytes. Several different parameters have been investigated, including the intrinsic chemical and physical properties of the nanophase (chemical composition, thermal conductivity, photo-absorption efficiency, specific heat capacity, phase transition point, explosion threshold, etc.), along with morphological parameters such as the nanophase size, shape, and interparticle distance. Other aspects, such as the composition, roughness and defects of the substrate supporting the LDI-active nanophases, the nanophase binding affinity towards the target analyte, the role of water molecules, have been taken into account as well. Readers interested in nanoparticle based LDI-MS sub-techniques (SALDI-, SELDI-, NALDI- MS) will find here a concise overview of the recent findings in the specialized field of fundamental and mechanistic studies, shading light on the desorption ionization phenomena responsible of the outperforming MS data offered by these techniques.

Highlights

  • Nowadays matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) [1]represents a versatile and important technique for the characterization of macromolecules as proteins, DNA, synthetic and bio-polymers [2,3]

  • The use of organic matrices introduces several drawbacks in MALDI-MS analysis such as: (i) problematical detection of low molecular weight compounds, due to background noise of matrix-related ions; (ii) absence of a universal matrix, which implies a preliminary knowledge of the investigated compounds; (iii) difficult quantitative analysis, due to inhomogeneous matrix-analyte co-crystallization

  • Surface assisted laser desorption/ionization (SALDI) MS was introduced by Sunner et al [4], who employed a matrix composed of a suspension of graphite particles in a blend of glycerol, sucrose, and methanol for the analysis of peptides

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Summary

Introduction

Nowadays matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) [1]represents a versatile and important technique for the characterization of macromolecules as proteins, DNA, synthetic and bio-polymers [2,3]. The use of organic matrices introduces several drawbacks in MALDI-MS analysis such as: (i) problematical detection of low molecular weight compounds (to approximately 700 m/z), due to background noise of matrix-related ions; (ii) absence of a universal matrix, which implies a preliminary knowledge of the investigated compounds; (iii) difficult quantitative analysis, due to inhomogeneous matrix-analyte co-crystallization. These and related problems encouraged the search for alternative approaches as matrix-free desorption/ionization methods. Materials such as metal oxide nanoparticles or silicon nanowires are scarcely ionized due to their high melting and boiling points, with a resulting limited production of interfering ions in the low mass

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