The electron impact (EI) mass spectra of a series of N,N-dialkyl-aminoethyl-2-chlorides, N(R(1))(R(2))-CH(2)-CH(2)Cl and trimethylsilyl ethers of N,N-dialkyl aminoethane-2-ols, N(R(1))(R(2))-CH(2)-CH(2)-O-Si(CH(3))(3), where R(1) and R(2) = methyl, ethyl, propyl and isopropyl, which are precursors of VX type of compounds, are studied. All the compounds (1-20) show abundant molecular ions, in addition to a weak [M - H](+) ion, except the N,N-diisopropyl group containing compounds (8 and 18). A general EI fragmentation pattern for the above two series of compounds is discussed. The observed fragment ions are due to simple homolytic cleavages, and they are distinct to allow the identification of the compounds unequivocally including those of isomeric compounds. The primary fragmentation of compounds 1-20 is beta-cleavage, i.e. homolytic cleavage of C-C bond, which is linked to the nitrogen atom. Three types of beta-cleavages are possible for these compounds, in which the abundance of beta-cleavage product ions is found to depend on the size and structure of the alkyl group attached to nitrogen. The alpha-cleavage fragment ions are found only for N,N-dialkyl aminoethyl-2-chlorides but are absent in the corresponding trimethylsilyl ethers of N,N-dialkyl aminoethane-2-ols. The retention indices are calculated for all the studied compounds (1-20) and are in the ranges of 750.38-1079.24 for 1-10 and 905.23-1190.25 for 11-20.

A set of DNA tetranucleotides, which are 3'- or 5'-end extended versions of GCA, was used as chiral selectors for the discrimination of enantiomers of alpha-amino acids. The [X+Y-2H](2-) ions of the 1:1 complexes were generated by electrospraying a mixture of tetranucleotide (X) and amino acid (Y) solution. Chiral discrimination was achieved by studying the collision-induced dissociation spectra of the [X+Y-2H](2-) ion and the ratio of relative abundance of precursor ion to that of the product ion was used to measure the extent of discrimination. Among the tetranucleotides used, GCAA and GGCA exhibited better discrimination, in which GCAA showed D-selectivity and GGCA showed L-selectivity for the studied amino acids. In addition, binding constants were measured for the 1:1 complexes of phenylalanine enantiomers with GCAA and GGCA. Ltd.

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Dimeric complex ions of the type [M(A-H)A]+, where M=metal ion (Co, Ni, Cu, and Zn) and A=ligand (lactic acid, methyl lactate or ethyl lactate), were generated in the gas phase under electrospray ionization conditions. The collision-induced dissociation spectra of [M(A-H)A]+ ions were recorded to study the behaviour of ligand and metal ions in decomposition of these dimeric complex ions. Based on the fragmentation pathways observed for complex ions of lactic acid, it is found that both the carboxylic and hydroxyl groups of lactic acid are involved in the complex formation following displacement of a proton by the metal ion. The dimeric complex ions of Co, Ni, and Zn dissociated to yield similar types of ions, whereas that of Cu behaved differently. The dissociations of Co-, Ni-, and Zn-bound dimeric complexes involved losses of neutral molecules while keeping the oxidation state of the metal ion unchanged. However, elimination of radicals is found in the dissociation of dimeric complex ions of Cu, and the oxidation state of copper is reduced from Cu(II) to Cu(I) in the resulting fragment ions. The deprotonated ligand is involved in the fragmentation pathway of Cu complexes, whereas it is intact in other complexes. The oxidation state of the metal ion, nature of the ligand, and site of attachment to the metal ion are found to control the dissociation of these dimeric complex ions.

The negative ion electrospray ionization (ESI) mass spectra of a series of dicarboxylic acids, a pair of isomeric (cis/trans) dicarboxylic acids and two pairs of isomeric (positional) substituted benzoic acids, including a pair of hydroxybenzoic acids, were recorded in the presence of halide ions (F(-), Cl(-), Br(-) and I(-)). The ESI mass spectra contained [M--H](-) and [M+X](-) ions, and formation of these ions is found to be characteristic of both the analyte and the halide ion used. The analytes showed a greater tendency to form adduct ions with Cl(-) under ESI conditions compared with the other halide ions used. The isomeric compounds yielded distinct spectra by which the isomers could be easily distinguished. The collision-induced dissociation mass spectra of [M+X](-) ions reflected the gas-phase basicities of both the halide ion and [M--H](-) ion of the analyte. However, the relative ordering of gas-phase basicities of all analyte [M--H](-) and halide ions could not account for the dominance of chloride ion adducts in ESI mass spectra of the analytes mixed with equimolar quantities of the four halides.