Laser microprobe mass spectrometry of quaternary phosphonium salts: direct versus matrix-assisted laser desorption

AbstractThe use of laser microprobe mass spectrometry (LMMS) for the structural characterization of thermolabile quaternary phosphonium salts has been evaluated. A comparison has been made between LM mass spectra obtained by direct analysis of “neat” organic salts and the corresponding “matrix-assisted” LM mass spectra. Main limitations of LMMS for the direct analysis of neat organic salts (i.e., no matrix) result from (1) formation of artifact ions that originate from thermal degradation and surface recombination reactions and (2) poor shot-to-shot reproducibility of the spectra. Dilution of the organic salts in a suitable, UV-absorbing matrix (e.g., nicotinic acid) significantly enhances the quality of the LM mass spectra. Improvements are: (1) an increase of the ion yield of preformed cations, 92) reduction or elimination of thermal decomposition and other deleterious surface reactions, and (3) a much better shot-to-shot spectral reproducibility. An interesting analytical feature is that these LM mass spectra, which contain only a few matrix peaks, can be obtained for subnanogram amounts of sample.The results also show that triphenylphosphonium salts with polycyclic aromatic substituents can be used as “molecular thermometers” to probe both the temperatures experienced by the sample molecules during the laser-induced sesorption ionization process and the internal energies of the desorbed ion species. In this way, quaternary phosphonium salts can be used for evaluating whether improvements have been achieved by applying different sample tretments. Comparison of four different matrices (i.e., nicotinic acid, ammonium chloride, glycerol, and 3-nitrobenzylalcohol) indicates that the effectiveness of a matrix to reduce thermal degradation and to decrese the internal energies of the ions depends on the UV-absorption characteristics and the volatilization/sublimation temperature of the matrix material

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,...). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state

Rapid evaporative ionization mass spectrometry for high throughput screening in food analysis : the case of boar taint

Boar taint is a contemporary off-odor present in meat of uncastrated male pigs. As European Member States intend to abandon surgical castration of pigs by 2018, this off-odor has gained a lot of research interest. In this study, rapid evaporative ionization mass spectrometry (REIMS) was explored for the rapid detection of boar taint in neck fat. Untargeted screening of samples (n=150) enabled discrimination between sow, tainted and untainted boars. The obtained OPLS-DA models showed excellent classification accuracy, i.e. 99% and 100% for sow and boar samples or solely boar samples, respectively. Furthermore, the obtained models demonstrated excellent validation characteristics (R2(Y)=0.872–0.969; Q2(Y)=0.756–0.917), which were confirmed by CV- ANOVA (p < 0.001) and permutation testing. In conclusion, in this work for the first time highly accurate and high-throughput ( < 10 s) classification of tainted and untainted boar samples was achieved, rendering REIMS a promising technique for predictive modelling in food safety and quality applications

Cov²MS: An Automated and Quantitative Matrix-Independent Assay for Mass Spectrometric Measurement of SARS-CoV-2 Nucleocapsid Protein

[Image: see text] The pandemic readiness toolbox needs to be extended, targeting different biomolecules, using orthogonal experimental set-ups. Here, we build on our Cov-MS effort using LC–MS, adding SISCAPA technology to enrich proteotypic peptides of the SARS-CoV-2 nucleocapsid (N) protein from trypsin-digested patient samples. The Cov(2)MS assay is compatible with most matrices including nasopharyngeal swabs, saliva, and plasma and has increased sensitivity into the attomole range, a 1000-fold improvement compared to direct detection in a matrix. A strong positive correlation was observed with qPCR detection beyond a quantification cycle of 30–31, the level where no live virus can be cultured. The automatable sample preparation and reduced LC dependency allow analysis of up to 500 samples per day per instrument. Importantly, peptide enrichment allows detection of the N protein in pooled samples without sensitivity loss. Easily multiplexed, we detect variants and propose targets for Influenza A and B detection. Thus, the Cov(2)MS assay can be adapted to test for many different pathogens in pooled samples, providing longitudinal epidemiological monitoring of large numbers of pathogens within a population as an early warning system