Accurate and reproducible ion mobility measurements for chemical standard evaluation.

Chemical standards are used to calibrate ion mobility spectrometers (IMS) for accurate and precise identification of target compounds. Research over the past 30 years has identified several positive and negative mode compounds that have been used as IMS standards. However, the IMS research community has not come to a consensus on any chemical compound(s) for use as a reference standard. Also, the reported K(0) values for the same compound analyzed on several IMS systems can be inconsistent. In many cases, mobility has not been correlated with a mass identification of an ion. The primary goal of this work was to provide mass-identified mobility (K(0)) values for standards. The results of this work were mass-identified K(0) values for positive and negative mode IMS chemical standards. The negative mode results of this study showed that TNT is a viable negative mode reference standard. New temperature-dependent K(0) values were found by characterizing drift gas temperature and water content; several examples were found of temperature-dependent changes for the ion species of several standards. The overall recommendation of this study is that proposed IMS standards should have temperature-dependent K(0) values quoted in the literature instead of using a single K(0) value for a compound.

Characterization of bacterial phospholipids by electrospray ionization tandem mass spectrometry.

A negative ion electrospray ionization tandem mass spectrometric technique was developed for the analysis of glycerophospholipids. Examination of the product ion mass spectrum of the deprotonated molecular ion provided sufficient information to identify both the class of glycerophospholipid and the molecular weights of the two fatty acid moieties. This technique was applied to the profiling of glycerophospholipids present in the chloroform/methanol extracts of four different bacterial species. The principal bacterial phospholipids detected by this technique were phosphatidylglycerols and diphosphatidylglycerols, accompanied by small amounts of phosphatidylethanolamines for two of the bacterial species examined. The fatty acid composition of the phosphatidylglycerols for each bacteria was determined by tandem mass spectrometry and presented graphically. Differences in the fatty acid composition for each bacterial species were readily apparent from a visual examination of the data sets.

On the structure of water-alcohol and ammonia-alcohol protonated clusters.

Collision-induced dissociation (CID) of protonated ammonia-alcohol and water-alcohol heteroclusters was studied using a triple quadrupole mass spectrometer with a corona discharge atmospheric pressure ionization source. CID results suggested that the ammonia-alcohol clusters had NH: at the core of the cluster and that hydrogen-bonded alcohol molecules solvated this central ion. In contrast, CID results in water-alcohol clusters showed that water loss was strongly favored over alcohol loss and that there was a preference for the charge to reside on an alcohol molecule. The results also indicated that a loose chain of hydrogen-bonded molecules was formed in the water-alcohol clusters and that there appeared to be no rigid protonation site or a fixed central ion. (J Am Soc Mass.

Ion mobility spectrometry of halothane, enflurane, and isoflurane anesthetics in air and respired gases.

Three common gaseous anesthetics, halothane, enflurane, and isoflurane, were characterized by using ion mobility spectrometry (IMS)/mass spectrometry, and the dependence of product ion distributions on temperature and concentration was evaluated. At 40 degrees C and 500 ppb, negative ion mobility spectra in air largely consisted of monomer or dimer adducts with Br- or Cl- formed through dissociative electron capture of molecular neutrals. With increased temperature or decreased vapor concentrations, declustering and dissociation of product ions became pronounced. Ion-molecule reactions in the drift region of the IMS were evident as distortions in peak shape in the mass-resolved mobility spectra and in variable reduced mobilities for the same ions. A portable hand-held IMS was used for convenient, real-time detection of enflurane in respired gases following a controlled inhalation episode.

Mass spectrometry of ion-induced water clusters: an explanation of the infrared continuum absorption.

Mass spectrometry was used to study ion-induced water clusters [H(+)(H(2)O)(c)], where c = the cluster size, i.e.,the number of monomers per cluster. It is shown that the numbers of hydrogen bonds in populations of these clusters in water vapor vary as the square of partial pressure and inversely with temperature, with functional dependencies that are almost identical to those observed for the infrared continuum absorption and for anomalous absorption in other wavelength regions. Experimental mass spectra taken at constant temperature vs partial pressure and data obtained at constant water vapor partial pressure vs temperature are presented and discussed. These results are combined with the evidence of cloud physicists including C. T. R. Wilson to show rather conclusively that naturally occurring ionic processes in water vapor generate large populations of hydrogen-bonded neutral water clusters that are responsible for the infrared continuum absorption. These processes can be enhanced by various kinds of ionizing energy, thus increasing anomalous absorption in water vapor or in moist air. If electrical properties of the atmosphere influence the infrared continuum absorption, which is an important mechanism in determining climate at the earth's surface, it will be necessary to reexamine extensively existing models of atmospheric radiative transfer.