Journal of the Mass Spectrometry Society of Japan
Online ISSN : 1880-4225
Print ISSN : 1340-8097
ISSN-L : 1340-8097
50 巻, 6 号
選択された号の論文の9件中1~9を表示しています
報文
  • Seiko NAKAGAWA
    2002 年 50 巻 6 号 p. 286-289
    発行日: 2002年
    公開日: 2007/10/16
    ジャーナル フリー
    The temperature dependence for the formation of negative ions from Cl2BrC-CBrCl2, FClBrC-CBrF2, and ClBr2C-CF3 was studied using negative chemical ionization mass spectrometry. Halide ions and halogen molecular anions were observed. The intensity ratios between the halide ions and halogen molecular anions were almost equal to F2BrC-CBrF2. Halogen molecular anions are produced from halogen atoms presented by each C atom: the four-center elimination. The temperature dependence of the ion intensity ratios, Br-/Cl- and Br2-/BrCl-, suggests that the strength of the bonding energy of the C-Cl relative to C-Br increases in the order of Cl2BrC-CBrCl2<FClBrC-CBrF2<ClBr2C-CF3.
  • Motohiro SHIZUMA, Hitoshi YAMADA, Hiroshi ADACHI, Yoshio TAKAI, Tokuji ...
    2002 年 50 巻 6 号 p. 290-295
    発行日: 2002年
    公開日: 2007/10/16
    ジャーナル フリー
    The FAB mass spectrometry (MS)/enantiomer labeled (EL) guest method is one of the useful technique to easily evaluate chiral discrimination ability of a chiral host (H) toward chiral guests (GR+, GS-dn+). In this paper, the matrix dependency of the relative peak intensity (IRIS) of the diastereomeric host-guest complex ions [(H+GR)+ and (H+GS-dn)+] was investigated (host, MeFruNys; guest, Phe-O-iPr+). The IRIS values of spectra measured using NBA, NPOE, and DTDE matrices agreed almost with the ratio of concentrations of the complex ions calculated from the association constants (KR and KS) in chloroform at 298 K. While, the IRIS values of spectra using glycerol matrix reached almost unity. It was assumed that the IRIS values depend upon the matrices used since the difference of solvation ability of the matrices affects the actual concentration of the guest concerning in the complexation. And then, it was recommended that NBA is the best matrix for chiral recognition mass spectrometry studies.
  • Jintao HUANG, Tomohiro FURUKAWA, Kazumi AOTO, Michio YAMAWAKI
    2002 年 50 巻 6 号 p. 296-300
    発行日: 2002年
    公開日: 2007/10/16
    ジャーナル フリー
    Electron impact ionization is a common way to provide positive ions for mass spectrometry. For most of molecular vapor species, however, experimental values of their electron impact ionization cross-sections are so limited that theoretic estimations become necessary. It is found that classic model such as additive rule or its modified version is no longer valid near the ionization threshold. Knowledge in this area is important for alkaline metals like sodium because their molecules may reach the maximum cross-section just a few eV above the ionization potential and easily crack in higher incident energies. A Binary-Encounter-Bethe (BEB) model developed by NIST was employed to calculate the cross-sections of NaO, NaOH, Na2, and Na2O molecules. The total ionization cross-section is computed from partial cross-sections of molecular orbitals. Gaussian and GAMESS code were employed to calculate the necessary molecular orbital parameters in the ground state. Calculated cross-sections were plotted as a function of electron impact energy. Reliability of the data predicted by BEB model was investigated by measuring corresponding ionization efficiency curves for some of the molecules. It was found that I(E)/Imax is generally equal to σ(E)/σmax within 15% in the testing range from 5 to 30 eV for sodium-containing molecules. It indicates that the BEB predictions seem correct at low electron incident energies.
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総合論文
  • 澤田 正實
    2002 年 50 巻 6 号 p. 311-329
    発行日: 2002年
    公開日: 2007/10/16
    ジャーナル フリー
    The developments of our quantitative chiral recognition studies in the host-guest complexations between chiral crown ethers and chiral amino acid esters by FAB, ESI, and MALDI mass spectrometry have been described. Both the enantiomer labeled (EL)-guest method and the EL-host method, which had been previously proposed by us, were successfully advanced. The relative peak intensity (IRIS) values of the diastereomeric host-guest complex ions appeared in mass spectra were especially noted, and their use to chiral recognition was illustrated. Generally, the former method was used to chiral recognition ability-determination of a given host, and the latter one was used to enantiomeric excess (e.e.)-determination of a given guest. Through the manuscript, emphasis has been put on the finding that one can detect correctly the concentration ratio of the two diastereomeric host-guest complex ions formed in a matrix solution by FAB mass spectrometry and then, that FABMS is a powerful tool for detecting chiral host-guest interactions in the host-guest complexation systems. Recent ,e.e.-determination methods by ESI mass spectrometry etc. were also summarized.
報文
速報
  • Hydrogen-Attachment Dissociation (HAD)
    高山 光男
    2002 年 50 巻 6 号 p. 337-349
    発行日: 2002年
    公開日: 2007/10/16
    ジャーナル フリー
    In-source decay (ISD) combined with matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometer (TOF MS) has been described by comparing with conventional mass spectrometric degradation (MSD) methods such as collision-induced dissociation (CID) and post-source decay (PSD). The ISD characteristic is the formation of c- and (z+2)-ions originated from the N-Cα bond cleavage on the peptide backbone, while the CID and PSD processes are the CO-NH bond cleavage which brings about b- and y-ion. Furthermore, the ISD processes occurring with 337 nm laser photon irradiation for peptide or protein proceed resulting in the formation of hyper-valent radical species via intermolecular hydrogen transfer between matrix and analyte molecules following the non-ergodic N-Cα bond cleavage. The non-ergodic N-Cα bond cleavage occurs in the MALDI ion source within nanosecond order, as an α-cleavage initiated with radical site at the carbonyl carbon. The MALDI-ISD method has been applied to three peptides and five proteins.
  • 渡辺 誠, 江口 大介, 佐藤 哲也, 平岡 賢三
    2002 年 50 巻 6 号 p. 350-352
    発行日: 2002年
    公開日: 2007/10/16
    ジャーナル フリー
    Secondary ions produced by 400 eV He+ ion impact on Ar, Kr, and Xe thin films deposited on a silicon substrate at 8 K were measured as a function of film thickness using a time-of-flight secondary-ion mass spectrometer. For Ar, the cluster ions Arn+ up to n=4 as well as the monomer ion (n=1) were observed and they showed characteristic film-thickness dependence with increase of the film thickness up to ~200 monolayers. This is due to the momentum transfer in the elastic collision between the incident He+ ion and the matrix Ar atoms and also to the relaxation of electronic excitations (e.g., holes and excitons) to phonons resulting in the film erosion. In contrast, neither dimer nor cluster ions were detected for solid Kr and Xe films. This is due to the less efficient momentum transfer in the elastic collision between He+ and Rg's (Rg=Kr and Xe) and also to the efficient electronic energy migration in solid Kr and Xe. The C+ ions originating from the carbonic contaminants on the silicon substrate were found to be sensitized by the deposition of rare gas films. The penetration depths of the primary ion He+ through the rare gas films increase in the order of Ar<Kr<Xe.
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