Dimethyl ether and dimethyl-d6 ether chemical ionization mass spectrometry of nitramines,nitroaromatics and related compounds

Dimethyl ether (DME) chemical ionization mass spectrometry with introduction by direct exposure desorption was utilized for the characterization of a variety of nitramines, nitroaromatics and related compounds. For the nitramines and for many of the nitroaromatics the most abundant ions were fragment-molecule adduct ions resulting from ion-molecule reactions with the reagent gas. Nitroaromatic positional isomers were readily distinguished by large differences in the abundances of the various adduct ions. For the nitramines, collision-induced dissociations of the prominent methoxymethylene adduct ions were studied and contrasted with those of the corresponding adducts derived from DME-d₆ as reagent gas.     

Stereochemical differentiation of cyclic glycols by ion-molecule reactions in a quadrupole mass spectrometer using dimethyl ether acetonitrile and 2-S-pyrrolidinemethanol

In this study, ion-molecule reactions using chemical ionization in the positive ion mode using dimethyl ether, acetonitrile and 2-S-pyrrolidinemethanol as reagent gases have been used to distinguish between cis- and trans-1,2-cyclopentanediol and cis- and trans-1,2-cyclohexanediol. In the gas phase, the stereospecific ion-molecule reaction gives characteristic ions and substantial differences are observed in their relative abundances from which the diastereoisomers of those cyclic glycols can be clearly differentiated. Copyright 2000 John Wiley & Sons, Ltd.     

Skeletal rearrangements on chemical ionization of dibenzyl ether and derivatives

Protonated molecular ions of dibenzyl ether, formed by chemical ionization using hydrogen and isobutane as reagent gases, undergo skeletal rearrangements to lose water and formaldehyde, both in the ion source and the flight path. The rearrangements have been elucidated by deuterium labelling and chemical substitution. The water lost contains the reagent proton and an aromatic hydrogen atom, and the aromatic hydrogen atoms have been shown to be mobile prior to the reaction. It is proposed that the skeletal rearrangement for water loss is initiated by protonation on the ether oxygen atom, followed by benzyl migration. The formaldehyde lost contains benzylic hydrogen atoms exclusively, and it is proposed that the skeletal rearrangement is preceded by hydrogen rearrangement of an oxygen protonated molecular ion to a ring protonated molecular ion. Daughter ion structures are supported by comparisons of their collision induced dissociation spectra with those of isomeric ions prepared by alternative routes.     

The location of olefinic bonds in mono- and di-unsaturated compounds

The use of vinyl methyl ether as a chemical ionization reagent gas for the location of olefinic bonds is limited by reactions of various ion with vinyl methyl ether molecules. A 75: 20: 5 mixture of nitrogen/carbon disulphide/vinyl methyl ether suggested by Harrison and Chai gives much cleaner spectra and has been used to study octenes and octadienes. Evidence is presented to indicate the formation of two reaction complexes with octenes and four reaction complexes with unconjugated octadienes. Elimination of olefins from these complexes allows one to infer the positions of the carbon-carbon double bonds in each type of molecule.     

Photodissociation of non-covalent peptide-crown ether complexes

Highly chromogenic 18-crown-6-dipyrrolylquinoxaline coordinates primary amines of peptides, forming non-covalent complexes that can be transferred to the gas-phase by electrospray ionization. The appended chromogenic crown ether facilitates efficient energy transfer to the peptide upon ultraviolet irradiation in the gas phase, resulting in diagnostic peptide fragmentation. Collisional-activated dissociation and infrared multiphoton dissociation of these non-covalent complexes result only in their disassembly with the charge retained on either the peptide or crown ether, yielding no sequence ions. Upon UV photon absorption the intermolecular energy transfer is facilitated by the fast activation timescale of ultraviolet photodissociation (<10 ns) and by the collectively strong hydrogen bonding between the crown ether and peptide, thus allowing effective transfer of energy to the peptide moiety before disruption of the intermolecular hydrogen bonds.     

Analysis of hydroxy fatty acids as pentafluorobenzyl ester,trimethylsilyl ether derivatives by electron ionization gas chromatography/mass spectrometry

Electron ionization (EI) gas chromatography/mass spectrometry (GC/MS) analysis of pentafluorobenzyl ester-trimethyl sllyl ether (PFB-TMS) derivatives of hydroxy-subshtuted fatty acids provides structural information comparable to that obtained in analysis of methyl ester-trimethyl silyl ether (Me-TMS) derivatives. Use of this derivative eliminates the need to prepare two separate derivatives, the PFB-TMS derivative for molecular weight determination by electron capture ionization (negative ions) analysis and the Me-TMS derivative for structural determination by EI GC/MS analysis. The relative abundance of fragment ions observed during EI GC/MS analysis of these derivatized unsaturated fatty acids indicates the location of the —OTMS substituents relative to double bond positions in those cases studied. The most abundant fragment ions are observed when the compound contains an unsaturation two carbon atoms removed from the —OTMS ether carbon (the β-OTMS position). The “saddle effect” observed in the GC/MS analyses of some derivatized monohy— droxy unsaturated fatty acids is suggested to be due to a thermally allowed pericyclic double bond rearrangement and indicates the presence of a conjugated diene one carbon atom removed from the —OTMS ether carbon (the α-OTMS position). The saddle effect is most prominent for fatty acids that contain additional unsaturation separated by a single methylene unit from the conjugated diene moiety.     

Probing the Effects of Reagent Gas Pressure and Ion Source Temperature for Dimethyl Ether Chemical Ionization of Tricyclic Antidepressants in an External Source Ion Trap Mass Spectrometer

This study examines the reagent gas pressure and ion source temperature dependence for dimethyl ether chemical ionization (DME CI) mass spectra recorded with an external source ion trap mass spectrometer (ITMS). Information for better controls of the reagent gas pressure in order to obtain fair CI spectra is provided. The origin of M^+? ions observed in DME CIMS is discussed in detail. Furthermore, the ion source temperature effect on the DME CI is also investigated.     

Separation of isomeric polycyclic aromatic hydrocarbons by GC-MS: Differentiation between isomers by positive chemical ionization with ammonia and dimethyl ether as reagent gases

Summary Sixteen PAHs have been separated by GC-MS and some isomeric PAHs were differentiated by positive-ion chemical ionization (PICI) using two different reagent gases, ammonia and dimethyl ether. Differentiation, which was better with DME, was possible on the basis of the identities and relative abundances of the adduct ions.     

FTIR analysis of dimethyl ether decomposition products following charge transfer ionization with Ar+ under matrix isolation conditions

Fourier transform infrared spectroscopic analysis has been performed on argon matrices formed following electron bombardment of argon/dimethyl ether mixtures. Products consistent with the ionization and subsequent fragmentation of dimethyl ether cation have been observed. Following ionization of dimethyl ether, fragmentation occurs that is consistent with ionization energy greater than 15 eV due to efficient charge transfer from dimethyl ether to Ar(+) as the major ionization process. Major products observed in the infrared spectra are methane, formaldehyde, HCO(*), CO, and Ar(2)H(+). These products are consistent with the known fragmentation of photoionized dimethyl ether in a 15-16 eV ionization energy range. However, the observation of dehydrogenated products is consistent with additional abstraction of hydrogen from proximally located species isolated within the matrix. Analogous experiments employing CD(3)OCH(3) give similar results, and the observed isotopically substituted products are consistent with the proposed fragmentation pathways.     

Generation of arylnitrenium ions by nitro-reduction and gas-phase synthesis of <Emphasis Type="Italic">N</Emphasis>-Heterocycles

Nitro-reduction by the vinyl halide radical cation CH2 = CH-X+* (X = Cl or Br) converts nitroaromatics into arylnitrenium ions, significant intermediates in carcinogenesis, and the present study reports on the scope and regioselectivity of this versatile reaction. The reaction is general for different kinds of substituted nitroaromatics; para/meta substitutents have little effect on the reaction while ortho substitutents result in low yields of arylnitrenium ions. The phenylnitrenium ion PhNH+ can be generated by chemical ionization (CI) of nitrobenzene using 1,2-dichloroethane as the reagent gas or by atmospheric pressure chemical ionization (APCI) of 1,2-dichloroethane solution doped with nitrobenzene. The chemical reactivities of the arylnitrenium ions include one-step ion/molecule reactions with nucleophiles ethyl vinyl ether and 1,3-dioxolanes, respectively, involving the direct formation of new CN bonds and synthesis of indole and benzomorpholine derivatives. The indole formation reaction parallels known condensed phase chemistry, while the concise morpholine-forming reaction remains to be sought in solution. The combination of collision-induced dissociation (CID) with novel ion/molecule reactions should provide a selective method for the detection of explosives such as TNT, RDX and HMX in mixtures using mass spectrometry. In addition to the reduction of the nitro group, reduction of methyl phenyl sulfone PhS(O)2Me to the thioanisole radical cation PhSMe+* occurs using the same chemical ionization reagent 1,2-dichloroethane. This probably involves an analogous reduction reaction by the reagent ion CH2 = CH-Cl+*.     

Determination of 3-methyl-2,4-nonanedione in red wines using methanol chemical ionization ion trap mass spectrometry

A compound associated with oxidized flavor in red wines was recently-identified as 3-methyl-2,4-nonanedione (MND). In order to quantify it, positive chemical ionization (PCI) in an ion trap was studied using conventional liquid reagents such as methanol, acetonitrile, and acetone, as well as non-conventional liquid reagents such as ethyl acetate, diethyl ether, pentane, isohexane, and heptane. Under laboratory conditions, very different response factors were obtained with MND depending on the gas. We also compared the detection limit of conventional CI with hybrid chemical ionization (HCI). Finally, this compound was quantified in red wines by liquid/liquid extraction without any derivatization steps, followed by GC/MS-CI analysis, using methanol as the reagent gas. Coelutions of compounds with the same m/z were checked using methanol-d(4). The method we developed was linear in the 10-300 ng/L range of MND concentrations, with satisfactory repeatability. The detection limit was 4.3 ng/L, over 3 times lower than the olfactory perception threshold of this compound (16 ng/L). The suitability of this method for assaying this diketone in red wine was demonstrated by the analyzing many wines from different vintages.     

Comparison of gas chromatographic and gas chromatographic/mass spectrometric techniques for the analysis of TNT and related nitroaromatic compounds

The use of capillary column gas chromatography and gas chromatography/mass spectrometry for the analysis of a series of standard solutions (0.1 to 10 μg/ml) of 2,4,6-trinitrotoluene (TNT) and eight other nitroaromatic components was evaluated. The techniques included gas chromatography with electron capture detection (GC/ECD), full scan and selected ion monitoring gas chromatography/mass spectrometry with electron impact ionization (EI/FS and EI/SIM), full scan and selected ion monitoring gas chromatography/mass spectrometry with positive ion chemical ionization using methane reagent gas (PICI/FS and PICI/SIM), and full scan and selected ion monitoring gas chromatography/mass spectrometry with negative ion chemical ionization using methane reagent gas (NICI/FS and NICI/SIM). The performance of the techniques was comapared by determining the linear response range, precision, and detection limits of the analyses.     

Nitric oxide-assisted atmospheric pressure corona discharge ionization for the analysis of automobile hydrocarbon emission species

Nitric oxide reagent gas has been found to improve the sensitivty and robustness of the atmospheric pressure corona discharge ionization (APCDI) process. Sensitivity has been increased by a factor of 20-100, depending on the compound, over APCDI without nitric oxide. The robustness (defined as the sensitivity to matrix interferences) of APCDI in the presence of water has been improved by a factor of 3 over normal APCDI. These improvements are due in part to a modification of the commercial inlet system and ionization chamber that allows the chamber and sample gases to be heated to 100 and 350 °C, respectively. Nitric oxide was chosen as the reagent gas because of the variety and selectivity of its interaction with hydrocarbons with differing functional groups. Product ions of nitric oxide ionization and their subsequent tandem mass spectra are presented and discussed for selected alkanes, alkenes, alkylbenzenes, alcohols, aldehydes, and an ether. A tandem mass spectrometry (unique parent ion-daughter ion transition) method was developed to quantify componds of specific interest in vehicle emissions. The absolute sensitivty for these compounds, under ideal conditions, was determined and ranges from 0.006 ppb for xylene (most sensitive) to 80 ppb for C₈ (or larger) normal alkanes. Routine sensitivity for real-world samples was in the single parts per billion range for aromatic and olefinic species. Potential applications include the real-time, on-line monitoring of selected hydrocarbons in automobile exhaust.     

Chemical ionization mass spectrometry of hydrofluorocarbons, hydrofluorocarbon ethers and perfluoroalkenes

Positive and negative chemical ionization (CI) mass spectrometry is studied for hydrofluorocarbons (HFCs), hydrofluorocarbon ethers (HFEs), and perfluoroalkenes (PFCs) using various kinds of reagent gas. While no quasi-molecular ion was observed under electron impact ionization for saturated MFCs, [M-F]⁺ is detected under CI conditions using methane as a reagent gas. Mechanisms for the generation of [M-F]⁺ are discussed. Furthermore, nitrogen monoxide can be used as a reagent gas to observe [M + NO]⁺ for many HFCs and HFEs. In negative mode chloroform is also available to generate [M + Cl]⁻ for HFCs and HFEs containing -CHF- groups.     

液相色谱-电喷雾质谱法分析脂肪醇聚氧乙烯醚硫酸钠

采用电喷雾质谱(ESI/MS)技术建立了脂肪醇聚氧乙烯醚硫酸钠(AES)的烷基碳链分布、乙氧基分布及平均EO数、平均相对分子质量的测定方法;采用液相色谱-电喷雾质谱(LC-ESI/MS)测定了AES中的游离十二烷基硫酸钠(SDS)的含量。将本方法应用于实际样品的测定,并与核磁共振法测得的平均EO数进行比较,二者的测定结果相当吻合,从而验证了本法的可靠性。     

Hydrolysis,methanolysis and ammonolysis of dicarboxylic acids and methyl esters under conditions of chemical ionization mass spectrometry

Chemical ionization mass spectra of dicarboxylic acids and methyl esters show fragmentation and unimolecular reactions with reagent gases water, methanol, ammonia and methyl ether, which differ from those observed with hydrocarbon reagents methane and isobutane. These reactions involve exchange of the reagent gas for water or methanol of the dicarboxyl compounds as well as secondary exchange of both functions. An effort has been made to determine the mechanism of these reactions and to determine the structural requirements necessary for their occurrence.     

Method for determination of methyl tert-butyl ether in gasoline by gas chromatography

A simple method for the determination of methyl tert-butyl ether (MTBE) in gasoline has been developed. The separation of MTBE from other analytes was controlled by the use of gas chromatography–mass spectrometry in the full scan mode using the characteristic primary, secondary and tertiary ions m/z 73, 57 and 43. The sample mass spectrum did not show any superimposition of other analytes. The separation from the common gasoline component 2-methylpentane was sufficient for reliable quantitation. An application of the developed conditions using gas chromatography with flame ionization detection was performed by the analysis of regular, euro super, super premium unleaded and ‘Optimax’ gasoline from petrol stations in the area of Frankfurt/Main, Germany. Regular unleaded gasoline shows an average MTBE content of 0.4% (w/w), whereas the MTBE content in euro super gasoline varies between 0.4 and 4.2% (w/w). The blending of MTBE to super premium has increased from 8.2% (w/w) in 1998 to 9.8% (w/w) on average in 1999. The recently introduced gasoline ‘Optimax’ shows an average MTBE content of 11.9% (w/w). The presented method might also be used for the analysis of other ethers, such as ethyl tert-butyl ether, which requires the use of another internal standard.     

Synthesis and properties of poly(ether ether ketone)-block-sulfonated polybutadiene copolymers for PEM applications

A novel series of sulfonated block copolymers were successfully synthesized by the condensation of modified poly(ether ether ketone) (PEEK) and polybutadiene (PB), followed by the selective post-sulfonation of PB blocks using acetyl sulfate as the sulfonating reagent. The sulfonic acid groups were only attached onto PB segments due to the high reactivity of double bonds to sulfonating reagent. The degree of sulfonation was controlled by changing the feed ratio of sulfonating reagent to block copolymer. PEEK-b-sPB could be easily cast into flexible and transparent membranes. The obtained membranes exhibited good thermal stability and satisfied mechanical properties. Tensile test showed the incorporation of sulfonate groups into PB blocks resulted in an increase in tensile strength and a decrease in elongation at break. TEM images revealed the existence of ionic spherical domains with the average sizes of 50-100 nm. Some of these small domains further aggregated to form large hydrophilic regions. The proton conductivity values were measured in the range of 10⁻² S/cm in water and increased with increasing IEC and temperature.     

Chemical ionization mass spectrometry of crown ether acetals using isobutane as reagent gas

Isobutane chemical ionization mass spectrometry of crown ether acetals (M), derived from ethanal, give [MH]⁺ ions from which species corresponding to 44 u are successively eliminated. Mechanisms are presented in which these units correspond to (i) ethanal and (ii) oxirane. An accompanying process is the elimination of ethyne. Similar reactions occur in the chemical ionization mass spectrometry of benzo crown ether acetals.     

Multiple-stage mass spectrometry analysis of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and their derivatives

The fragmentation of bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether (BFDGE) and their derivatives was studied by electrospray ionization tandem mass spectrometry. Multiple-stage mass spectrometry and accurate mass measurements were combined to establish the fragmentation pathways. BADGEs and BFDGEs tend to form ammonium adducts under electrospray conditions which fragmented easily. The fragmentation of [M+NH(4)](+) for BADGEs started with the cleavage of the phenyl-alkyl bond, which was followed by the α-cleavage of the ether group to generate the characteristic product ions at m/z 135, [C(9)H(11)O](+), and m/z 107, [C(7)H(7)O](+). The fragmentation of the BFDGE isomer mixtures was studied by on-line reversed-phase liquid chromatography coupled to multiple-stage mass spectrometry (LC/MS(n)). Information obtained from product ion spectra for each BFDGE isomer and its comparison with the fragmentation pathway of BADGE allowed each isomer and the chromatographic elution order to be identified.