Tandem ion mobility spectrometry at ambient pressure and field decomposition of mobility selected ions of explosives and interferences.

A tandem ion mobility spectrometer at ambient pressure included a thermal desorption inlet, two drift regions, dual ion shutters, and a wire grid assembly in the second drift region. An ion swarm could be mobility isolated in the first drift region using synchronized dual ion shutters and decomposed in a wire grid assembly using electric fields of 1.80 × 104 V cm-1 (118 Td) from a 1.8 MHz sinusoidal waveform. Mobility selected ions that underwent field induced decomposition were NO3-, from PETN·Cl- and NG·Cl-, and NO2- from RDX·Cl-. The extent of decomposition ranged from 60 to 90%, depending on gas temperature, field strength, and ion identity, introducing additional controls to improve selectivity in trace determination of explosives. Ion transmission through the wire grid assembly ranged from 80 to >95% with losses increasing for increased field strength. Studies with pairs of explosives and interfering substances demonstrated decisive detection of explosives and portend reduced rates of false positive using tandem ion mobility spectrometers with a reactive stage.

Constituents with independence from growth temperature for bacteria using pyrolysis-gas chromatography/differential mobility spectrometry with analysis of variance and principal component analysis.

Four bacteria, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus warneri, and Micrococcus luteus, were grown at temperatures of 23, 30, and 37 degrees C and were characterized by pyrolysis-gas chromatography/differential mobility spectrometry (Py-GC/DMS) providing, with replicates, 120 data sets of retention time, compensation voltage, and ion intensity, each for negative and positive polarity. Principal component analysis (PCA) for 96 of these data sets exhibited clusters by temperature of culture growth and not by genus. Analysis of variance was used to isolate the constituents with dependences on growth temperature. When these were subtracted from the data sets, Fisher ratios with PCA resulted in four clusters according to genus at all temperatures for ions in each polarity. Comparable results were obtained from unsupervised PCA with 24 of the original data sets. The ions with taxonomic features were reconstructed into 3D plots of retention time, compensation voltage, and Fisher ratio and were matched, through GC-mass spectrometry (MS), with chemical standards attributed to the thermal decomposition of proteins and lipid A. Results for negative ions provided simpler data sets than from positive ions, as anticipated from selectivity of gas phase ion-molecule reactions in air at ambient pressure.

Analysis of bacteria by pyrolysis gas chromatography-differential mobility spectrometry and isolation of chemical components with a dependence on growth temperature.

Pyrolysis gas chromatography-differential mobility spectrometry (py-GC-DMS) analysis of E. coli, P. aeruginosa, S. warneri and M. luteus, grown at temperatures of 23, 30, and 37 degrees C, provided data sets of ion intensity, retention time, and compensation voltage for principal component analysis. Misaligned chromatographic axes were treated using piecewise alignment, the impact on the degree of class separation (DCS) of clusters was minor. The DCS, however, was improved between 21 to 527% by analysis of variance with Fisher ratios to remove chemical components independent of growth temperature. The temperature dependent components comprised 84% of all peaks in the py-GC-DMS analysis of E. coli and were attributed to the pyrolytic decomposition of proteins rather than lipids, as anticipated. Components were also isolated in other bacteria at differing amounts: 41% for M. luteus, 14% for P. aeruginosa, and 4% for S. warneri, and differing patterns suggested characteristic dependence on temperature of growth for these bacteria. These components are anticipated to have masses from 100 to 200 Da by inference from differential mobility spectra.

Analysis of bacterial strains with pyrolysis-gas chromatography/differential mobility spectrometry.

Eight vegetative bacterial strains and two spores were characterized by pyrolysis-gas chromatography with differential mobility spectrometry (py-GC/DMS) yielding topographic plots of ion intensity, retention time, and compensation voltage simultaneously for ions in positive and negative polarity. Biomarkers were found in the pyrolysate at characteristic retention times and compensation voltages and were confirmed by standard addition with GC/MS analyses providing discrimination between Gram negative and Gram positive bacterial types, but no recognition of individual strains within the Gram negative bacteria. Principal component analysis was applied using two dimensional data sets of ion intensity versus retention time at five compensation voltages including the reactant ion peaks all in positive and negative ion polarity. Clustering was observed with compensation voltage (CV) chromatograms associated with ion separation in the DMS detector and little or no clustering was observed with the reactant ion peaks or CV chromatograms where ion separation is poor. Consistent clustering of Gram positive B. odysseyi and Gram negative E. coli in both positive and negative polarities with the reactant ion peak chromatograms and key CV chromatograms suggests common but unknown common chemical compositions in the pyrolysate.

Microfabricated differential mobility spectrometry with pyrolysis gas chromatography for chemical characterization of bacteria.

A microfabricated drift tube for differential mobility spectrometry (DMS) was used with pyrolysis-gas chromatography (py-GC) to chemically characterize bacteria through three-dimensional plots of ion intensity, compensation voltage from differential mobility spectra, and chromatographic retention time. The DMS analyzer provided chemical information for positive and negative ions simultaneously from chemical reactions between pyrolysis products in the GC effluent and reactant ions of H+(H2O)n and O2-(H2O)n in air at ambient pressure. Authentic standards for chemicals formed in the pyrolysis of bacteria showed favorable matches with plots from py-GC/DMS analysis and were supported by py-GC/MS results. These and other yet-unidentified constituents provided a means to distinguish Escherichia coli from Micrococcus luteus. A Gram-positive spore former (Bacillus megaterium) was distinguished by an abundant peak for crotonic acid evident in positive and negative ions and not observed with M. luteus. In contrast, plots from py-GC/DMS of lipid A and lipoteichoic acid showed poor matches to plots for a Gram-negative (E. coli) bacterium and a Gram-positive (M. luteus) bacterium and the differences were attributed to differences in genus sources of the biopolymers. A significant percentage of the chemical information available in py-GC/DMS is unidentified, and the analytical utility must be established. Precision in the chemical measurement was determined as +/- 0.2 V, 10% relative standard deviation (RSD), and +/- 0.05 min for compensation voltage, peak intensity, and retention time, respectively. The minimum number of total bacteria (cell forming units) detected was 6000 though detection limits and resolution could be varied by the magnitude of the separation voltage in the differential mobility spectrometer.

Detection of the gasoline components methyl tert-butyl ether, benzene, toluene, and m-xylene using ion mobility spectrometers with a radioactive and UV ionization source.

For the first time, ion mobility spectrometers (IMS) with radioactive and UV ionization sources in combination with multicapillary columns (MCCs) have been used to determine methyl tert-butyl ether (MTBE), a gasoline additive, in water and nitrogen as well as the monoaromatic compounds benzene, toluene, and m-xylene (BTX). A membrane extraction unit was set up to extract the substances from water, which is simple, effective, and easy to automate for further applications. Thus, the detection of MTBE and BTX of gasoline vapors was accomplished after a preliminary silicone membrane extraction. Two-dimensional data analyses of IMS-chromatograms allow us to separate these substances clearly according to their different retention and drift times. Method detection limits for MTBE were 2 microg/L (UV) and 30 pg/L (63Ni) in nitrogen and 20 mg/L (UV) and 1 microg/L (63Ni) in water. Rather a good reproducibility was achieved with relative standard deviations of between 2.9 and 9%. The method presented in this article has been proven to be suitable for nearly real-time monitoring as the total analysis time is less than 90 s. As an example of application, the detection of MTBE and BTX in a mixture of volatile organic compounds of pure gasoline using the 2-D IMS-chromatogram is presented.