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Yasuo Seto - One of the best experts on this subject based on the ideXlab platform.

  • identification of v type nerve agents in vapor samples using a field portable capillary gas chromatography membrane interfaced Electron Ionization quadrupole mass spectrometry instrument with tri bed concentrator and fluoridating conversion tube
    Journal of Mass Spectrometry, 2017
    Co-Authors: Yasuhiko Ohrui, Tomoki Nagoya, Naoko Kurimata, Manabu Sodeyama, Yasuo Seto
    Abstract:

    A field-portable gas chromatography-mass spectrometry (GC-MS) system (Hapsite ER) was evaluated for the detection of nonvolatile V-type nerve agents (VX and Russian VX (RVX)) in the vapor phase. The Hapsite ER system consists of a Tri-Bed concentrator gas sampler, a nonpolar low thermal-mass capillary GC column and a hydrophobic membrane-interfaced Electron Ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump. The GC-MS system was attached to a VX-G fluoridating conversion tube containing silver nitrate and potassium fluoride. Sample vapors of VX and RVX were converted into O-ethyl methylphosphonofluoridate (EtGB) and O-isobutyl methylphosphonofluoridate (iBuGB), respectively. These fluoridated derivatives were detected within 10 min. No compounds were detected when the VX and RVX samples were analyzed without the conversion tube. A vapor sample of tabun (GA) was analyzed, in which GA and O-ethyl N,N-dimethylphosphoramidofluoridate were detected. The molar recovery percentages of EtGB and iBuGB from VX and RVX vapors varied from 0.3 to 17%, which was attributed to variations in the vaporization efficiency of the glass vapor container. The conversion efficiencies of the VX-G conversion tube for VX and RVX to their phosphonate derivatives were estimated to be 40%. VX and RVX vapors were detected at concentrations as low as 0.3 mg m-3 . Gasoline vapor was found to interfere with the analyses of VX and RVX. In the presence of 160 mg m-3 gasoline, the detection limits of VX and RVX vapor were increased to 20 mg m-3 . Copyright © 2017 John Wiley & Sons, Ltd.

  • identification of chemical warfare agents from vapor samples using a field portable capillary gas chromatography membrane interfaced Electron Ionization quadrupole mass spectrometry instrument with tri bed concentrator
    Journal of Chromatography A, 2015
    Co-Authors: Hisayuki Nagashima, Tomoki Nagoya, Naoko Kurimata, Tomohide Kondo, Toru Ikeda, Shohei Unoke, Yasuo Seto
    Abstract:

    A field-portable gas chromatograph-mass spectrometer (Hapsite ER system) was evaluated for the detection of chemical warfare agents (CWAs) in the vapor phase. The system consisted of Tri-Bed concentrator gas sampler (trapping time: 3s(-1)min), a nonpolar low thermal-mass capillary gas chromatography column capable of raising temperatures up to 200°C, a hydrophobic membrane-interfaced Electron Ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump for data acquisition, and a personal computer for data analysis. Sample vapors containing as little as 22μg sarin (GB), 100μg soman (GD), 210μg tabun (GA), 55μg cyclohexylsarin (GF), 4.8μg sulfur mustard, 390μg nitrogen mustard 1, 140μg of nitrogen mustard 2, 130μg nitrogen mustard 3, 120μg of 2-chloroacetophenone and 990μg of chloropicrin per cubic meter could be confirmed after Tri-Bed micro-concentration (for 1min) and automated AMDIS search within 12min. Using manual deconvolution by background subtraction of neighboring regions on the extracted ion chromatograms, the above-mentioned CWAs could be confirmed at lower concentration levels. The memory effects were also examined and we found that blister agents showed significantly more carry-over than nerve agents. Gasoline vapor was found to interfere with the detection of GB and GD, raising the concentration limits for confirmation in the presence of gasoline by both AMDIS search and manual deconvolution; however, GA and GF were not subject to interference by gasoline. Lewisite 1, and o-chlorobenzylidene malononitrile could also be confirmed by gas chromatography, but it was hard to quantify them. Vapors of phosgene, chlorine, and cyanogen chloride could be confirmed by direct mass spectrometric detection at concentration levels higher than 2, 140, and 10mg/m(3) respectively, by bypassing the micro-concentration trap and gas chromatographic separation.

Younis Abiedalla - One of the best experts on this subject based on the ideXlab platform.

  • differentiation of cyclic tertiary amine cathinone derivatives by product ion Electron Ionization mass spectrometry
    Rapid Communications in Mass Spectrometry, 2016
    Co-Authors: Younis Abiedalla, Karim M Abdelhay, Jack Deruiter, Randall C Clark
    Abstract:

    RATIONALE: A number of synthetic cathinones (aminoketones, 'bath salts') are tertiary amines containing a cyclic amino group, most commonly pyrrolidine. These totally synthetic compounds can be prepared in a number of regioisomeric designer modifications and many of these can yield isomeric major fragment ions in Electron Ionization mass spectrometry (EI-MS). METHODS: A series of regioisomeric cyclic tertiary amines were prepared and evaluated in EI-MS and MS/MS product ion experiments. The cyclic amines azetidine, pyrrolidine, piperidine and azepane were incorporated into a series of aminoketones related to the cathinone derivative drug of abuse known as MDPV. Deuterium labeling in both the cyclic amine and alkyl side chain allowed for the confirmation of the structure for the major product ions formed from the EI-MS iminium cation base peaks. RESULTS: These iminium cation base peaks show characteristic product ion spectra which allow differentiation of the ring and side-chain portions of the structure. The small alkyl side chains favor ring fragmentation in the formation of the major product ions. The higher side-chain homologues appear to promote product ion formation by side-chain fragmentation. Both side-chain and ring fragmentation yield a mixture of product ions in the piperidine and azepane series. CONCLUSIONS: Product ion fragmentation provides useful data for differentiation of cyclic tertiary amine iminium cations from cathinone derivative drugs of abuse. Regioisomeric iminium cations of equal mass yield characteristic product ions for the alkyl side-chain homologues of azetidine, pyrrolidine, piperidine and azepane cyclic amines.

  • differentiation of cyclic tertiary amine cathinone derivatives by product ion Electron Ionization mass spectrometry
    Rapid Communications in Mass Spectrometry, 2016
    Co-Authors: Younis Abiedalla, Karim M Abdelhay, Jack Deruiter, Randall C Clark
    Abstract:

    RATIONALE: A number of synthetic cathinones (aminoketones, 'bath salts') are tertiary amines containing a cyclic amino group, most commonly pyrrolidine. These totally synthetic compounds can be prepared in a number of regioisomeric designer modifications and many of these can yield isomeric major fragment ions in Electron Ionization mass spectrometry (EI-MS). METHODS: A series of regioisomeric cyclic tertiary amines were prepared and evaluated in EI-MS and MS/MS product ion experiments. The cyclic amines azetidine, pyrrolidine, piperidine and azepane were incorporated into a series of aminoketones related to the cathinone derivative drug of abuse known as MDPV. Deuterium labeling in both the cyclic amine and alkyl side chain allowed for the confirmation of the structure for the major product ions formed from the EI-MS iminium cation base peaks. RESULTS: These iminium cation base peaks show characteristic product ion spectra which allow differentiation of the ring and side-chain portions of the structure. The small alkyl side chains favor ring fragmentation in the formation of the major product ions. The higher side-chain homologues appear to promote product ion formation by side-chain fragmentation. Both side-chain and ring fragmentation yield a mixture of product ions in the piperidine and azepane series. CONCLUSIONS: Product ion fragmentation provides useful data for differentiation of cyclic tertiary amine iminium cations from cathinone derivative drugs of abuse. Regioisomeric iminium cations of equal mass yield characteristic product ions for the alkyl side-chain homologues of azetidine, pyrrolidine, piperidine and azepane cyclic amines.

Walter Vetter - One of the best experts on this subject based on the ideXlab platform.

  • gas chromatography Electron Ionization mass spectrometry selected ion monitoring screening method for a thorough investigation of polyhalogenated compounds in passive sampler extracts with quadrupole systems
    Analytical Chemistry, 2010
    Co-Authors: Natalie Rosenfelder, Nathan J Van Zee, Jochen F Mueller, Caroline Gaus, Walter Vetter
    Abstract:

    Nontarget analysis and identification of unknown polyhalogenated compounds is important in acquiring a thorough picture of the present pollution status as well as for identifying emerging environmental problems. Such analyses usually require the application of Electron Ionization mass spectrometry because the resulting mass spectra frequently allow for compound identification. When quadrupoles are used as mass separators, the full scan technique often suffers from low sensitivity along with nonspecificity for polyhalogenated trace compounds which often result in interference by matrix compounds. We have developed a novel nontarget gas chromatography/Electron Ionization-mass spectrometry-selected ion monitoring (GC/EI-MS-SIM) method that overcomes these sensitivity and selectivity issues. Our method is based on the fact that the molecular ions and isotope patterns of polyhalogenated compounds involve the most relevant primary information with regard to the structure of polyhalogenated compounds. Additional...

  • determination of polybrominated biphenyls in tasmanian devils sarcophilus harrisii by gas chromatography coupled to Electron capture negative ion tandem mass spectrometry or Electron Ionization high resolution mass spectrometry
    Rapid Communications in Mass Spectrometry, 2008
    Co-Authors: Walter Vetter, Roland Von Der Recke, R Symons, Stephen Pyecroft
    Abstract:

    Two gas chromatography/mass spectrometry (GC/MS) methods for the determination of polybrominated biphenyls (PBBs) by isotope dilution analysis (IDA) using (13)C(12)-PBB 153 in the presence of polybrominated diphenyl ethers (PBDEs) were compared. Recovery of (13)C(12)-PBB 153 which was added to the extracted lipids before sample purification was commenced ranged from 88-117% (mean value 98.2 +/- 8.9%). Nevertheless, IDA analysis of PBBs using (13)C(12)-labelled congeners is limited by the potential co-elution of PBBs with polybrominated diphenyl ethers (PBDEs). The pair PBB 153 and BDE 154 was inspected since M(+) and [M-2Br](+) ions of (13)C(12)-PBB 153 and BDE 154 were only separated by 4 u. Gas chromatography/Electron Ionization high-resolution mass spectrometry with selected ion monitoring (GC/EI-HRMS-SIM) was suitable when m/z 475.7449 and m/z 477.7429 were used for (13)C(12)-PBB 153 because they are below the monoisotopic peak of the [M-2Br](+) fragment ion of hexaBDEs at m/z 479.7. Gas chromatography/Electron capture negative ion tandem mass spectrometry selected reaction monitoring (GC/ECNI-MS/MS-SRM) measurements could be applied because (13)C(12)-PBB 153 and BDE 154 were separated by GC on a 25-m Factor Four CP-Sil 8MS column.Comparative measurements with GC/EI-HRMS-SIM and GC/ECNI-MSMS-SRM were carried out with samples of Tasmanian devils from Tasmania (Australia), an endangered species due to a virus epidemy which has already proved fatal for half of the population. Both techniques verified concentrations of PBB 153 in the range 0.3-11 ng/g lipids with excellent agreement of the levels in all but two samples. The PBB residue pattern demonstrated that PBB pollution originated from the previous discharge with technical hexabromobiphenyl which is dominated by PBB 153. Other congeners such as PBB 132 and PBB 138 were detected in the Tasmanian devils but the proportions relative to PBB 153 were lower than in the technical product. Samples of healthy and affected Tasmanian devils showed no significant difference in the PBB pollution level. The PBB concentrations in the Tasmanian devils were significantly below those causing toxic effects. On the other hand, PBB concentrations were one level or even higher than PBDEs.

  • a gas chromatography Electron Ionization mass spectrometry selected ion monitoring method for determining the fatty acid pattern in food after formation of fatty acid methyl esters
    Journal of Agricultural and Food Chemistry, 2005
    Co-Authors: Saskia Thurnhofer, Walter Vetter
    Abstract:

    A method using gas chromatography/Electron Ionization−mass spectrometry (GC/EI-MS) in the selected ion monitoring (SIM) mode was developed for the analysis of fatty acids as methyl esters (FAMEs) in order to determine their percentage contribution to the fatty acid profile in food. In the GC/EI-MS-SIM mode, saturated fatty acids were determined with m/z 87, monoenoic fatty acids were determined with m/z 74, and polyenoic fatty acids were determined via the sum of m/z 79 and m/z 81. The ratios of these fragment ions and the GC retention data provided additional information for tentative structural assignments. The 28 FAME standards tested provided similar results for the novel GC/EI-MS-SIM method and GC/EI-MS in the full scan mode, both of which were slightly worse than GC/flame Ionization detection (FID). Analysis of sunflower oil, suet, and cod liver oil verified that both major and minor fatty acids (20−60% and down to 0.001% contribution to the fatty acid pattern) were determined with sufficient qualit...

  • a gas chromatography Electron Ionization mass spectrometry selected ion monitoring method for determining the fatty acid pattern in food after formation of fatty acid methyl esters
    Journal of Agricultural and Food Chemistry, 2005
    Co-Authors: Saskia Thurnhofer, Walter Vetter
    Abstract:

    A method using gas chromatography/Electron Ionization-mass spectrometry (GC/EI-MS) in the selected ion monitoring (SIM) mode was developed for the analysis of fatty acids as methyl esters (FAMEs) in order to determine their percentage contribution to the fatty acid profile in food. In the GC/EI-MS-SIM mode, saturated fatty acids were determined with m/z 87, monoenoic fatty acids were determined with m/z 74, and polyenoic fatty acids were determined via the sum of m/z 79 and m/z 81. The ratios of these fragment ions and the GC retention data provided additional information for tentative structural assignments. The 28 FAME standards tested provided similar results for the novel GC/EI-MS-SIM method and GC/EI-MS in the full scan mode, both of which were slightly worse than GC/flame Ionization detection (FID). Analysis of sunflower oil, suet, and cod liver oil verified that both major and minor fatty acids (20-60% and down to 0.001% contribution to the fatty acid pattern) were determined with sufficient quality that justifies application of the GC/EI-MS-SIM method for the analysis of food samples. Furthermore, the method was approximately 20- or approximately 10-fold more sensitive than GC/EI-MS in the full scan mode or GC/FID, respectively. The method is suited for both quantitative purposes and fatty acid identification in samples where only low amounts of lipids are available.

Aviv Amirav - One of the best experts on this subject based on the ideXlab platform.

  • Electron Ionization lc ms with supersonic molecular beams the new concept benefits and applications
    Journal of Mass Spectrometry, 2015
    Co-Authors: Boaz Seemann, Alexander B Fialkov, Tal Alon, Svetlana Tsizin, Aviv Amirav
    Abstract:

    A new type of Electron Ionization LC-MS with supersonic molecular beams (EI-LC-MS with SMB) is described. This system and its operational methods are based on pneumatic spray formation of the LC liquid flow in a heated spray vaporization chamber, full sample thermal vaporization and subsequent Electron Ionization of vibrationally cold molecules in supersonic molecular beams. The vaporized sample compounds are transferred into a supersonic nozzle via a flow restrictor capillary. Consequently, while the pneumatic spray is formed and vaporized at above atmospheric pressure the supersonic nozzle backing pressure is about 0.15 Bar for the formation of supersonic molecular beams with vibrationally cold sample molecules without cluster formation with the solvent vapor. The sample compounds are ionized in a fly-though EI ion source as vibrationally cold molecules in the SMB, resulting in 'Cold EI' (EI of vibrationally cold molecules) mass spectra that exhibit the standard EI fragments combined with enhanced molecular ions. We evaluated the EI-LC-MS with SMB system and demonstrated its effectiveness in NIST library sample identification which is complemented with the availability of enhanced molecular ions. The EI-LC-MS with SMB system is characterized by linear response of five orders of magnitude and uniform compound independent response including for non-polar compounds. This feature improves sample quantitation that can be approximated without compound specific calibration. Cold EI, like EI, is free from ion suppression and/or enhancement effects (that plague ESI and/or APCI) which facilitate faster LC separation because full separation is not essential. The absence of ion suppression effects enables the exploration of fast flow injection MS-MS as an alternative to lengthy LC-MS analysis. These features are demonstrated in a few examples, and the analysis of the main ingredients of Cannabis on a few Cannabis flower extracts is demonstrated. Finally, the advantages of EI-LC-MS with SMB are listed and discussed.

  • classical Electron Ionization mass spectra in gas chromatography mass spectrometry with supersonic molecular beams
    Rapid Communications in Mass Spectrometry, 2008
    Co-Authors: Alexander Gordin, Alexander B Fialkov, Aviv Amirav
    Abstract:

    A major benefit of gas chromatography/mass spectrometry (GC/MS) with a supersonic molecular beam (SMB) interface and its fly-through ion source is the ability to obtain Electron Ionization of vibrationally cold molecules (cold EI), which show enhanced molecular ions. However, GC/MS with an SMB also has the flexibility to perform ‘classical EI’ mode of operation which provides mass spectra to mimic those in commercial 70 eV Electron Ionization MS libraries. Classical EI in SMB is obtained through simple reduction of the helium make-up gas flow rate, which reduces the SMB cooling efficiency; hence the vibrational temperatures of the molecules are similar to those in traditional EI ion sources. In classical EI-SMB mode, the relative abundance of the molecular ion can be tuned and, as a result, excellent identification probabilities and very good matching factors to the NIST MS library are obtained. Classical EI-SMB with the fly-through dual cage ion source has analyte sensitivity similar to that of the standard EI ion source of a basic GC/MS system. The fly-through EI ion source in combination with the SMB interface can serve for cold EI, classical EI-SMB, and cluster chemical Ionization (CCI) modes of operation, all easily exchangeable through a simple and quick change (not involving hardware). Furthermore, the fly-through ion source eliminates sample scattering from the walls of the ion source, and thus it offers full sample inertness, tailing-free operation, and no ion-molecule reaction interferences. It is also robust and enables increased column flow rate capability without affecting the sensitivity. Copyright © 2008 John Wiley & Sons, Ltd.

  • classical Electron Ionization mass spectra in gas chromatography mass spectrometry with supersonic molecular beams
    Rapid Communications in Mass Spectrometry, 2008
    Co-Authors: Alexander Gordin, Alexander B Fialkov, Aviv Amirav
    Abstract:

    A major benefit of gas chromatography/mass spectrometry (GC/MS) with a supersonic molecular beam (SMB) interface and its fly-through ion source is the ability to obtain Electron Ionization of vibrationally cold molecules (cold EI), which show enhanced molecular ions. However, GC/MS with an SMB also has the flexibility to perform ‘classical EI’ mode of operation which provides mass spectra to mimic those in commercial 70 eV Electron Ionization MS libraries. Classical EI in SMB is obtained through simple reduction of the helium make-up gas flow rate, which reduces the SMB cooling efficiency; hence the vibrational temperatures of the molecules are similar to those in traditional EI ion sources. In classical EI-SMB mode, the relative abundance of the molecular ion can be tuned and, as a result, excellent identification probabilities and very good matching factors to the NIST MS library are obtained. Classical EI-SMB with the fly-through dual cage ion source has analyte sensitivity similar to that of the standard EI ion source of a basic GC/MS system. The fly-through EI ion source in combination with the SMB interface can serve for cold EI, classical EI-SMB, and cluster chemical Ionization (CCI) modes of operation, all easily exchangeable through a simple and quick change (not involving hardware). Furthermore, the fly-through ion source eliminates sample scattering from the walls of the ion source, and thus it offers full sample inertness, tailing-free operation, and no ion-molecule reaction interferences. It is also robust and enables increased column flow rate capability without affecting the sensitivity. Copyright © 2008 John Wiley & Sons, Ltd.

  • lc ms with Electron Ionization of cold molecules in supersonic molecular beams
    International Journal of Mass Spectrometry, 2005
    Co-Authors: Ori Granot, Aviv Amirav
    Abstract:

    A new approach is described for the combination of Electron Ionization and LC–MS based on sample Ionization as vibrationally cold molecules in a supersonic molecular beam (Cold EI). Cold EI of sample compounds in liquid solutions (methanol, acetonitrile, water, etc.) is achieved through spray formation, followed by soft thermal vaporization of the sample particles prior to their supersonic expansion and direct Electron Ionization of the sample compounds while they are contained in a supersonic molecular beam (SMB). Cold EI mass spectra were demonstrated to combine an enhanced molecular ion and improved mass spectral information (in comparison with standard EI), plus all the library searchable fragments. Cold EI enables the Ionization of a broad range of compounds, including the full range of non-polar samples. Four orders of magnitude linear dynamic range is demonstrated and a detection limit of 2 pg was achieved for a 774 amu compound in single ion monitoring mode at m/z = 774. The method and apparatus are under continuous development and we feel that it can excel particularly in the analysis of unknown samples, while enabling fast LC–MS analysis through automated mass spectral deconvolution of coeluting LC peaks. In addition, the same MS system can also serve as an advanced GC–MS with supersonic molecular beams. © 2005 Elsevier B.V. All rights reserved.

  • improved Electron Ionization ion source for the detection of supersonic molecular beams
    Review of Scientific Instruments, 2002
    Co-Authors: Aviv Amirav, Alexander B Fialkov, Alexander Gordin
    Abstract:

    An improved Electron Ionization (EI) ion source is described, based on the modification of a Brink-type EI ion source through the addition of a second cage with a fine mesh outside the ion chamber. The added outer cage shields the inner ion cage (Ionization zone) against the penetration of the filament and Electron repeller potentials, and thus results in the provision of ions with narrower ion energy distribution, hence improved ion-beam quality. The closer to zero electrical field inside the ion cage enables improved filtration (rejection) of ions that are produced from vacuum background compounds, based on difference in ion energies of beam and background species. The improved background ion filtration and ion-beam quality resulted in 2.6 times higher mass spectrometric ion signal, combined with 6.4 times better signal to noise ratio, in comparison with the same ion source having a single cage. The dual cage ion source further provides a smaller or no reduction of the Electron emission current upon low...

Randall C Clark - One of the best experts on this subject based on the ideXlab platform.

  • differentiation of cyclic tertiary amine cathinone derivatives by product ion Electron Ionization mass spectrometry
    Rapid Communications in Mass Spectrometry, 2016
    Co-Authors: Younis Abiedalla, Karim M Abdelhay, Jack Deruiter, Randall C Clark
    Abstract:

    RATIONALE: A number of synthetic cathinones (aminoketones, 'bath salts') are tertiary amines containing a cyclic amino group, most commonly pyrrolidine. These totally synthetic compounds can be prepared in a number of regioisomeric designer modifications and many of these can yield isomeric major fragment ions in Electron Ionization mass spectrometry (EI-MS). METHODS: A series of regioisomeric cyclic tertiary amines were prepared and evaluated in EI-MS and MS/MS product ion experiments. The cyclic amines azetidine, pyrrolidine, piperidine and azepane were incorporated into a series of aminoketones related to the cathinone derivative drug of abuse known as MDPV. Deuterium labeling in both the cyclic amine and alkyl side chain allowed for the confirmation of the structure for the major product ions formed from the EI-MS iminium cation base peaks. RESULTS: These iminium cation base peaks show characteristic product ion spectra which allow differentiation of the ring and side-chain portions of the structure. The small alkyl side chains favor ring fragmentation in the formation of the major product ions. The higher side-chain homologues appear to promote product ion formation by side-chain fragmentation. Both side-chain and ring fragmentation yield a mixture of product ions in the piperidine and azepane series. CONCLUSIONS: Product ion fragmentation provides useful data for differentiation of cyclic tertiary amine iminium cations from cathinone derivative drugs of abuse. Regioisomeric iminium cations of equal mass yield characteristic product ions for the alkyl side-chain homologues of azetidine, pyrrolidine, piperidine and azepane cyclic amines.

  • differentiation of cyclic tertiary amine cathinone derivatives by product ion Electron Ionization mass spectrometry
    Rapid Communications in Mass Spectrometry, 2016
    Co-Authors: Younis Abiedalla, Karim M Abdelhay, Jack Deruiter, Randall C Clark
    Abstract:

    RATIONALE: A number of synthetic cathinones (aminoketones, 'bath salts') are tertiary amines containing a cyclic amino group, most commonly pyrrolidine. These totally synthetic compounds can be prepared in a number of regioisomeric designer modifications and many of these can yield isomeric major fragment ions in Electron Ionization mass spectrometry (EI-MS). METHODS: A series of regioisomeric cyclic tertiary amines were prepared and evaluated in EI-MS and MS/MS product ion experiments. The cyclic amines azetidine, pyrrolidine, piperidine and azepane were incorporated into a series of aminoketones related to the cathinone derivative drug of abuse known as MDPV. Deuterium labeling in both the cyclic amine and alkyl side chain allowed for the confirmation of the structure for the major product ions formed from the EI-MS iminium cation base peaks. RESULTS: These iminium cation base peaks show characteristic product ion spectra which allow differentiation of the ring and side-chain portions of the structure. The small alkyl side chains favor ring fragmentation in the formation of the major product ions. The higher side-chain homologues appear to promote product ion formation by side-chain fragmentation. Both side-chain and ring fragmentation yield a mixture of product ions in the piperidine and azepane series. CONCLUSIONS: Product ion fragmentation provides useful data for differentiation of cyclic tertiary amine iminium cations from cathinone derivative drugs of abuse. Regioisomeric iminium cations of equal mass yield characteristic product ions for the alkyl side-chain homologues of azetidine, pyrrolidine, piperidine and azepane cyclic amines.