Journal of the Mass Spectrometry Society of Japan
Online ISSN : 1880-4225
Print ISSN : 1340-8097
ISSN-L : 1340-8097
46 巻, 5 号
選択された号の論文の7件中1~7を表示しています
報文
  • 和田 芳直
    1998 年 46 巻 5 号 p. 429-432
    発行日: 1998年
    公開日: 2007/07/20
    ジャーナル フリー
    Achievement of the unit mass accuracy in the molecular mass determination of proteins has been stressed. Single mass change of proteins is caused by single amino acid substitutions including Glu/Lys, Asn/Leu, Asn/Ile, Asp/Asn, and Glu/Gln, of which four mutations except for Asn/Leu are produced by single nucleotide changes. In the case of Hemoglobin Hoshida, a substitution of Asn for Asp was found in a peptide of 2056.9 Da with a decrease of single mass unit. In a structural study of the transferrin isoform which is characteristic of carbohydrate-deficient glycoprotein syndrome and missing asparagine-linked oligosaccharides, assignment of Asn but not Asp for the residue that should be glycosylated was necessary for delineating the molecular pathogenesis of this disorder. However, as demonstrated in β2-microglobulin, proteins are often partially deamidated during sample preparation or in vivo. This may compromise the biological significance of the precise mass measurement of proteins.
  • 佐藤 貴弥, 伊藤 啓行, 市原 敏雄, 交久瀬 五雄, 松尾 武清
    1998 年 46 巻 5 号 p. 433-436
    発行日: 1998年
    公開日: 2007/07/20
    ジャーナル フリー
    Mass spectra of doubly charged tellurium clusters were investigated by a secondary ion mass spectrometry. Cluster ions were produced by the Xe ions bombardment on the tellurium sheet and were mass-analyzed using a grand-scale sector type mass spectrometer. Te22+, Te32+, and Te52+ were observed.
  • Toru SAKURAI, Takekiyo MATSUO
    1998 年 46 巻 5 号 p. 437-441
    発行日: 1998年
    公開日: 2007/07/20
    ジャーナル フリー
    A new computer code ‘TRIO-TOF’ has been constructed. The code can calculate ion flight times in time-of-flight (TOF) mass spectrometers to a third-order approximation. Ion-optical characteristics and focusing properties of time-of-flight mass spectrometers, which consist of toroidal electrostatic condensers and electrostatic quadrupole lenses, can be estimated by this code. The influences of the fringing field on ion flight times have been taken into consideration. The precise calculation of ion flight times in the fringing-fields has been also described.
  • Kenzo HIRAOKA, Takashi SHODA, Shinichi YAMABE, Edgar W. IGNACIO
    1998 年 46 巻 5 号 p. 442-447
    発行日: 1998年
    公開日: 2007/07/20
    ジャーナル フリー
    Gas-phase ion-molecule reactions have been investigated using a pulsed-electron beam mass spectrometer. The proton affinity (PA) of tetrahydrothiophene (THT), C4H8S, has been newly determined to be 205.4 kcal mol-1 by measuring the equilibria of the proton transfer reaction between 2-methyltetrahydrofuran and THT. The thermochemical data for the hydration reaction of protonated tetrahydrothiophene, C4H8SH+(H2O)n-1 + H2O=C4H8SH+(H2O)n, with n=1-3 were measured. The small and n-insensitive enthalpy changes (-ΔHn-1, n°), 11.5, 10.4 and 9.5 kcal mol-1, with n=1, 2, and 3, respectively, have been obtained. The fall-off of -ΔHn-1, n° vs. n is small due to the positive charge dispersal in the protonated THT. The rate of proton transfer reaction from the proton-hydrates H3O+(H2O)n to THT was found to be roughly the collision rate in agreement with the findings due to Viggiano et al. [J. Chem. Phys., 88, 2469 (1988)]. Ab initio calculations have been carried out, and those energies (PA and ΔHn-1, n°) have been reproduced satisfactorily.
  • Masao FUJISHIGE, Yohsuke SHIRAISHI, Osamu SEKIGUCHI, Susumu TAJIMA
    1998 年 46 巻 5 号 p. 448-453
    発行日: 1998年
    公開日: 2007/07/20
    ジャーナル フリー
    The unimolecular decompositions of the metastable ions produced from 2,2,2-trifluoroethyl acetate, CH3COOCH2CF3, 1, (Mw: 142), 2,2,2-trifluoroethyl trifluoroacetate, CF3COOCH2CF3, 2, (Mw: 196), and S-ethyl trifluorothioacetate, CF3COSCH2CH3, 3, (Mw: 158) upon electron ionization have been investigated by means of mass-analyzed ion kinetic energy (MIKE) spectrometry and D-labeling. The metastable ions 1+ decompose exclusively to give the ion at m/z 122 by losing HF via an 1,2-elimination.
    In the normal mass spectrum of 2, no molecular ion is observed, while the ion corresponding to the loss of CF3 gives rise to an intense peak at m/z 127 (about 90% of the base peak) and the ion corresponding to the loss of F gives the peak at m/z 177 with moderate intensity (about 20%). Both ions consist of two isomeric ions. Some interesting rearrangement processes, such as CF3 or OCH2CF3 migration followed by the loss of a CO molecule, occur during the metastable fragmentations of these ions.
    The molecular ion of 3, which is a base peak, decomposes into the ions at m/z 89 and 61 by losing CF3 and CF3CO, respectively, in the metastable time region. The relative abundance of ions in the MIKE spectrum are rationalized with the thermochemical data estimated by the PM 3 method.
  • Yoshiyuki MOCHIDA, Yukio YOKOYAMA, Shigeo NAKAMURA
    1998 年 46 巻 5 号 p. 454-458
    発行日: 1998年
    公開日: 2007/07/20
    ジャーナル フリー
    The effects of amines on the formation of molecular adduct ions of methyl hydroperoxyoleates (OMH) in atmospheric pressure chemical ionization mass spectrometry were investigated. The short-chain primary amines such as methylamine and ethylamine were more effective than ammonia on suppressing the thermal decomposition of OMH, and provided abundant [M+H+L]+ type ions (L: each amine molecule). The secondary and tertiary amines were unsuitable for the purpose in spite of their high basicity, probably due to the steric interference. Aromatic and heterocyclic amines were also ineffective. The formation of amine adduct to OMH in liquid and/or condensed phases depends on both basicity and stereochemistry of each amine.
解説
feedback
Top