Abstract
Intact (whole) cell matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS) is an established method for biotyping in clinical microbiology as well as for revealing phenotypic shifts in cultured eukaryotic cells. Intact cell MALDI-TOF MS has recently been introduced as a quality control tool for long-term cultures of pluripotent stem cells. Despite the potential this method holds for revealing minute changes in cells, there is still a need for improving the ionization efficiency or peak reproducibility. Here we report for the first time that supplementation by fine particles of black phosphorus to the standard MALDI matrices, such as sinapinic and α-cyano-4-hydroxycinnamic acids enhance intensities of mass spectra of particular amino acids and peptides, presumably by interactions with aromatic groups within the molecules. In addition, the particles of black phosphorus induce the formation of small and regularly dispersed crystals of sinapinic acid and α-cyano-4-hydroxycinnamic acid with the analyte on a steel MALDI target plate. Patterns of mass spectra recorded from intact cells using black phosphorus-enriched matrix were more reproducible and contained peaks of higher intensities when compared to matrix without black phosphorus supplementation. In summary, enrichment of common organic matrices by black phosphorus can improve discrimination data analysis by enhancing peak intensity and reproducibility of mass spectra acquired from intact cells.
Highlights
Intact cell matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF Mass spectrometry (MS)) is an established method for biotyping in clinical microbiology as well as for revealing phenotypic shifts in cultured eukaryotic cells
An insight on stability and homoatomic interactions of elemental phosphorus in MS was previously provided by Sládková et al.5 who investigated the generation of phosphorus clusters Pn (n = 1–89) from red phosphorus covering the range of mass up to 3000 m/z by applying laser desorption ionization (LDI) technique in both positive and negative ion modes and proposed that clusters of red phosphorus can serve as a useful calibration tool in MS
We have recently demonstrated that intact cell MALDI-TOF MS can provide a useful tool for the quality control in long-term cultures of human embryonic stem cells
Summary
Intact (whole) cell matrix-assisted laser desorption/ionization mass spectrometry (MALDI-TOF MS) is an established method for biotyping in clinical microbiology as well as for revealing phenotypic shifts in cultured eukaryotic cells. The black phosphorus (BP) is a highly stable allotrope that can form homoatomic supermolecular structures, e.g., cages or layers It has been described by He et al recently, that BP enhances ionization of analytes labelled by quaternary ammonium groups, most probably by nanoparticle- or surface-associated effects. This approach was claimed to be highly suitable for analysis of body fluids, such as saliva, urine, or blood serum, and quantitation of aldehyde species therein. Wang et al proposed a rapid and sensitive method for the determination of chemical labelled glucose serum using black phosphorus as a matrix in time-of-flight mass s pectrometry4 It is highly probable, that phosphorus effects in MS are linked to its nanostructure. It was suggested that this interaction is mediated by the electron transfer process from phosphorene to amino and carboxylic functional groups of amino acid molecules
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