Novel Ion Trap Scan Modes to Develop Criteria for On-Site Detection of Sulfonamide Antibiotics

Abstract

Advances in ambient ionization techniques have facilitated the direct analysis of complex mixtures without sample preparation. Significant attention has been given to innovating ionization methods so that multiple options are now available, allowing for ready selection of the best methods for particular analyte classes. These ambient techniques are commonly implemented on benchtop systems, but their potential application with miniature mass spectrometers for in situ measurements is even more powerful. These applications require that attention be paid to tailoring the mass spectrometric methodology for the on-site operation. In this study, combinations of scan modes are employed to efficiently determine what tandem mass spectrometry (MS/MS) operations are most useful for detecting sulfonamides using a miniature ion trap after ionization. First, mixtures of representative sulfonamide antibiotics were interrogated using a 2D MS/MS scan on a benchtop ion trap in order to determine which class-specific fragments (ionic or neutral) are shared between the sulfonamides and thus have diagnostic value. Then, three less-used combination scans were recorded: (i) a simultaneous precursor ion scan was used to detect both analytes and an internal standard in a single ion injection event to optimize quantitative performance; (ii) a simultaneous precursor/neutral loss scan was used to improve detection limits; and finally, (iii) the simultaneous precursor/neutral loss scan was implemented in a miniature mass spectrometer and representative sulfonamides were detected at concentrations as low as 100 ng/mL by nano-electrospray and 0.5 ng absolute by paper spray ionization, although improvements in the stability of the home-built instrumentation are needed to further optimize performance.

Metabolomic and Lipidomic Profiling of Bacillus Using Two-Dimensional Tandem Mass Spectrometry

“…This approach allows the capture of all precursor ion/product ion information in the 2D MS/MS data domain in times on the order of 1.2 s per scan using a single population of trapped ions. 2D MS/MS has previously been applied to monitoring bacterial lipid profiles and their changes over time, as well as for the analysis of complex mixtures of fentanyls and sulfonamides. , Two-dimensional mass spectrometry was initially reported in 1987 by Gäumann and co-workers and others using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) . Two-dimensional mass spectrometry (2D-MS) has been applied since in the analysis of polymers, top-down/bottom-up analysis of calmodulin, and bottom-up analysis of IgG 1 antibodies .…”

Rapid Identification of Phenolics in Mixtures by Two‐Dimensional Tandem Mass Spectrometry with Microdroplet Accelerated Derivatization Reactions

“…2D MS/ MS has been used to analyze mixtures of fentanyls, chemical warfare agents, sulfonamides in milk, as well as lipids and metabolites in bacterial lysates. [1,5,[8][9][10] 2D MS/MS spectra display ion abundances for product ions with m/z values (Pro m/z) given on the y-axis and their corresponding precursor ions with m/z values (Pre m/z) given on the x-axis of the 2D plot (Figure 1B). All fragment ions resulting from collision-induced dissociation (CID) are represented by peaks that fall below the auto-correlation line where Pre m/z = Pro m/z.…”

Miniature mass spectrometer-based point-of-care assay for measuring phosphatidylethanol in blood

“…[24][25][26] Most significantly, the combination of ambient ionization methods (analysis of native sample with minimal workup) with miniature mass spectrometers provides a particularly powerful solution for analysis of complex samples. [26][27][28][29][30][31][32][33][34][35] Despite the large number of instruments that have been made available and the success of many of these systems, much work remains to perform rapid bioanalysis of complex matrices such as blood, where analyte concentrations often lie in the ng mL −1 range.…”