The Sensitive High Resolution Ion MicroProbe (SHRIMP) is the first ion microprobe dedicated to geological isotopic analyses, especially in-situ analyses related to the geochronology of zircon. Such a sophisticated ion probe, which can attain a high sensitivity at a high mass resolution, based on a double focusing high mass-resolution spectrometer, designed by Matsuda (1974), was constructed at the Australian National University. In 1996, such an instrument was installed at Hiroshima University and was the first SHRIMP to be installed in Japan. Since its installation, our focus has been on the in-situ U-Pb dating of the mineral apatite, as well as zircon, which is a more common U-bearing mineral. This provides the possibility for extending the use of in-situ U-Pb dating from determining the age of formation of volcanic, granitic, sedimentary and metamorphic minerals to the direct determination of the diagenetic age of fossils and/or the crystallization age of various meteorites, which can provide new insights into the thermal history on the Earth and/or the Solar System. In this paper, we review the methodology associated with in-situ apatite dating and our contribution to Earth and Planetary Science over the past 16 years.
The backbone flexibility of a protein has been studied from the standpoint of the susceptibility of amino acid residues to in-source decay (ISD) in matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS). Residues more susceptible to MALDI-ISD, namely Xxx–Asp/Asn and Gly–Xxx, were identified from the discontinuous intense peak of c′-ions originating from specific cleavage at N–Cα bonds of the backbone of equine cytochrome c. The identity of the residues susceptible to ISD was consistent with the known flexible backbone amides as estimated by hydrogen/deuterium exchange (HDX) experiments. The identity of these flexible amino acid residues (Asp, Asn, and Gly) is consistent with the fact that these residues are preferred in flexible secondary structure free from intramolecular hydrogen-bonded structures such as α-helix and β-sheet. The MALDI-ISD spectrum of equine cytochrome c gave not only intense N-terminal side c′-ions originating from N–Cα bond cleavage at Xxx–Asp/Asn and Gly–Xxx residues, but also C-terminal side complement z·-ions originating from the same cleavage sites. The present study implies that MALDI-ISD can give information about backbone flexibility of proteins, comparable with the protection factors estimated by HDX.
Mucin-type O-glycosylation is a major posttranslational modification of proteins. The level of O-glycosylation at a site could be useful in terms of evaluating various disease conditions. To address the feasibility of measuring O-glycosylation levels based on the glycopeptide ion intensity in a mass spectrum, apoliporotein CIII (apoC3), a protein that contains a single core-1 O-glycan Gal–GalNAc disaccharide was analyzed by matrix-assisted laser desorption ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). The intensity of protonated ions for an equimolar mixture of desialylated and deglycosylated apoC3s were the same in linear TOF measurements. No substantial in-source decay, including the cleavage of the protein-sugar linkage was observed. The glycopeptide derived from apoC3 and the unglycosylated counterpart, when analyzed by MALDI reflectron TOF MS indicated that post-source decay was minimal. These collective findings demonstrate the feasibility of label-free quantitation of O-glycan occupancy by MS when the glycans are small and neutral. This method provides a tool for use in glycoproteomics as a complement of our previous report (DOI: 10.1021/pr900913k) for calculating the saccharide composition of O-glycans.
The construction of a small-size, magnetic sector, single focusing mass spectrometer (He-MS) for the continuous, on-site monitoring of He isotope ratios (3He/4He) is described. The instrument is capable of measuring 4He/20Ne ratios dissolved in several different types of natural fluids of geochemical interest, such as groundwater and gas from hot springs, volcanoes and gas well fields. The ion optics of He-MS was designed using an ion trajectory simulation program “TRIO,” which permits the simultaneous measurement of 3He and 4He with a double collector system under a mass resolution power (M/ΔM) of >500. The presently attained specifications of the He-MS are; (1) a mass resolving power of ca. 490, sufficient to separate 3He+ from interfering ions, HD+ and H3+, (2) ultra-high vacuum conditions down to 3×10−8 Pa, and (3) a sufficiently high sensitivity to permit amounts of 3He to be detected at levels as small as 10−13 cm3STP (3×106 atoms). Long term stability for 3He/4He analysis was examined by measuring the 3He/4He standard gas (HESJ) and atmospheric He, resulting in ∼3% reproducibility and ≤5% experimental error for various amounts of atmospheric He from 0.3 to 2.3×10−6 cm3STP introduced into the instrument. A dynamic range of measurable 3He/4He ratios with He-MS is greater than 103 which was determined by measuring various types of natural fluid samples from continental gas (with a low 3He/4He ratio down to 2×10−8) to volcanic gas (with a high 3He/4He ratio up to 3×10−5). The accuracy and precision of 3He/4He and 4He/20Ne ratios were evaluated by comparing the values with those measured using well established noble gas mass spectrometers (modified VG5400/MS-III and -IV) in our laboratory, and were found to be in good agreement within analytical errors. Usefulness of the selective extraction of He from water/gas using a high permeability of He through a silica glass wall at high temperature (700°C) is demonstrated.
A chemical tag at the peptide N-terminus, in combination with MS, can be useful for quantitative analysis, N-terminal peptide identification, or peptide sequencing. Here we report on the Nα selective acetylation of a peptide using acetic anhydride, a popular reagent for the modification of amino groups, without the need for the blocking of lysine side-chain ε-amino groups, which is usually required for Nα selective acetylation. By controlling the amount of acetic anhydride used and running the reaction at 0°C, it is possible to preferentially acetylate the α-amino group. As a typical application of the method, a tryptic digest of an N-terminally blocked protein, cytochrome c, was directly acetylated using the present method. When deuterated acetic anhydride was used as the reagent, the N-terminal blocked peptide could be easily identified as a non-labeled ion peak while the Nα-acetyl groups of all the other peptides were deuterated.
Correlations between chemical compositions and chromatographic retention times (Rt) of methacrylate random copolymers were studied by liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS). Twenty-six different polymers including homopolymers of poly(methyl methacrylate) (PMMA), poly(tert-butyl methacrylate) (PTBMA) and poly(2-hydroxyethyl methacrylate) (PHEMA), and their random copolymers of P(MMA-TBMA) and P(MMA-HEMA) with known chemical compositions were studied. The results indicate that there is close correlations between the chemical compositions of the random copolymers and their Rt of the C8 column in the mass spectral ranges of m/z 1,800–2,000. The LC-ESI-MS analysis showed molecular weights of the copolymers distribute in the mass range of ca. 500–20,000, and the structures of polymer terminals and their monomer units can be identified.
In this paper, we report the use of mass spectrometry imaging and structural analysis of lipids directly on a tissue specimen, carried out by means of matrix-assisted laser desorption/ionization tandem time-of-flight mass spectrometry, using a combination of spiral orbit-type and reflectron-type time-of-flight mass spectrometers. The most intense peak observed in the mass spectrum from a brain tissue specimen was confirmed as phosphatidylcholine (34:1) [M+K]+, using tandem mass spectrometry. The charge remote fragmentation channels, which are characteristically observed using high-energy collision-induced dissociation, contributed significantly to this confirmation. Accurate mass analysis was further facilitated by mass correction using the confirmed peak. In mass spectrometry imaging, the high resolving power of our system could separate doublet peak of less than 0.1 u difference, which would otherwise be problematic when using a low-resolution reflectron type time-of-flight mass spectrometer. Two compounds, observed at m/z 848.56 and 848.65, were found to be located in complementary positions on a brain tissue specimen. These results demonstrate the importance of a high-performance tandem time-of-flight mass spectrometer for mass spectrometry imaging and analysis of observed compounds, to allow distinction between biological molecules.
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