BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 63, Issue 3
Special Articles : Analytical Chemistry on Origin and History
Displaying 1-13 of 13 articles from this issue
Reviews
  • Makoto UEKI
    Article type: Reviews
    2014 Volume 63 Issue 3 Pages 161-169
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    Abuses of performance-enhancing agents and the manipulation or cheating of test systems are prohibited in order to protect fairness in sports and athletes’ health according to ethical considerations. Doping control is applied worldwide at all levels of sports. Recent trends of test results show that doping with naturally occurring substances, such as androgenic steroids, the pro-hormones and the metabolites, peptide hormones, blood and blood components etc. are increasing, so that the testing methods for origin identification must fit for the purpose depending on the property of the target compounds. This review refers to up-dated information concerning the procedures for origin identification of doping agents with special focus on GC-online isotope ratio mass spectrometry.
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Accounts
  • Issei MAEDA, Shunsuke FURUYA, Willy Shun Kai BONG, Yoshinari ABE, Keii ...
    Article type: Accounts
    2014 Volume 63 Issue 3 Pages 171-193
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    We have started to construct a nationwide forensic soil sediment database for Japan, based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3024 points across Japan. Each sample was measured by high-resolution synchrotron radiation X-ray powder diffraction (SR-XRD) analysis and high-energy SR X-ray fluorescence analysis (XRF) at SPring-8, the SR radiation facility in Japan. The automated sampling systems allow us to measure 130 powder diffraction patterns and 130 XRF spectra per day, respectively using the sediment samples of only a few milligrams, which enabled us to construct a database of a large number of samples. The concentrations of heavy elements such as rare earth elements, Cs and W in soil sediments can be determined by the calibration curve method by using high-energy SR-XRF utilizing monochromatic X-rays of 116 keV. A heavy element concentration map superimposed on a geographical map of Japan was successfully prepared from these analytical data. The heavy mineral compositions were semi-quantitatively evaluated by using the peak intensity of the characteristic XRD peaks of the component minerals measured by a Debye–Scherrer camera having a radius of 286.5 mm, recorded with an imaging plate and monochromatic X-rays (λ = 1.0 Å). This study demonstrates that these XRF and XRD data collected from sediments of Chiba, Kofu, Shizuoka and Shikoku region well reflect the geological and geographical signature of the sediment samples, which can be used for a provenance estimation of soil evidence from a crime scene.
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  • Keita YAMADA, Alexis GILBERT, Naohiro YOSHIDA
    Article type: Accounts
    2014 Volume 63 Issue 3 Pages 195-203
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    A stable isotopic composition in materials has provided useful information concerning their origins and histories. For a carbon isotopic measurement of a single organic molecule, the total organic carbon contained in the molecule should be converted quantitatively to carbon dioxide. Therefore, the carbon isotopic composition represents an average value for the molecules. In principle, information concerning the origins and histories of organic molecules exists at the specific position of the molecule. To retrieve diverse, complex, and specific information of their origins and histories from organic molecules, a measurement of the position-specific carbon isotopic composition is required. So far, a difficult measurement have prevented any development for the position-specific isotopic measurement. Here, we describe recent advances in analytical instrumentation concerning a position-specific carbon isotopic measurement for organic molecules using gas chromatography-combustion-isotope ratio mass spectrometry combined with an on-line pyrolysis technique.
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  • Kaoru ARIYAMA
    Article type: Accounts
    2014 Volume 63 Issue 3 Pages 205-220
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    Food labeling with a geographical identification gathers considerable concern from consumers, and is key information to select commodities. However, such labeling has sometimes been used fraudulently for financial gain. Thus, correct labeling is needed to maintain the reliability of food. Geographical identification is also used for a brandying strategy purpose. To maintain a brand with a high advantage, fraudulent labeling has to be eliminated. Various studies that scientifically determine the geographical origin of food have been conducted for the purpose of detecting erroneous indication. Techniques based on multielement composition obtained by inductively coupled plasma mass spectrometry were put into the first practical use as an origin-determination-technique in Japan. In this paper, the techniques are expounded on how to have been developed. As other factors, heavy element isotopic ratios permit reliable determination, because the exchangeable isotopic ratios of a habitat can be transferred to crops without mass fractionation. Since a technique with isotopic ratios of Sr and Pb as heavy elements eventually had reached practical applications, the latest research achievements are introduced in the article.
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  • Yuko T. IWATA, Kenji KUWAYAMA, Kenji TSUJIKAWA, Tatsuyuki KANAMORI, Hi ...
    Article type: Accounts
    2014 Volume 63 Issue 3 Pages 221-231
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    We review our studies of drug profiling of methamphetamine, the most abused drug in Japan, in this article. Drug profile was defined as a set of specific characteristics selected to provide information on the drug sources and histories, such as starting materials, synthetic routes and clandestine manufacturing. We developed a method for methamphetamine impurity-profiling using capillary gas chromatography. Impurities were extracted from methamphetamine hydrochloride with an organic solvent under alkaline conditions, and detected very well with good resolution. Using four internal standards improved the correction of retention times for inter-day or inter-laboratory comparisons of chromatograms. We also investigated the simultaneous chiral separation of 9 amphetamine-type stimulants that include methamphetamine and the precursors by capillary electrophoresis. The enantiomers were well resolved, and small peaks of the precursor impurities (i.e. ephedrines) of methamphetamine were detectable by analyzing the solution. We also investigated an evaluation method for linking MA seizures using stable isotope ratio mass spectrometry, and the usefulness of crystal-level profiling analysis was shown. Combining the several analyses revealed detail drug profiles, and enabled to acquire much more information on linking or discriminating seizures as well as the clandestine manufacturing of the drug.
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  • Takashi KORENAGA
    Article type: Accounts
    2014 Volume 63 Issue 3 Pages 233-244
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    The multi-stable isotopic analysis method has been employed as a potential powerful tool to solve food authenticity problems. Stable isotopic compositions and elemental contents of the H, C, N, and O in large numbers of rice samples, mostly Koshihikari, were analyzed by elemental analysis/isotope ratio mass spectrometry. The samples were taken from four different farming countries, such as Japan, U. S. A., Australia, and China. They were mostly of the short-grain variety, including several samples of middle and long grains, grown in the presence of either natural manure or artificial fertilizer. The climate of the rice-farming environment was diverse from arid to humid. Including δD data showing large uncertainty in Niigata prefecture, on the basis of principle-component analysis of the δ13C, δ15N, and δ18O of the rice samples, Japanese Koshihikari rice samples were clearly distinctive from any of the Australian rice samples and moderately different from most of the American rice samples. This fact may be influenced by a difference in the climate, soil nutrition, and/or quality of irrigation water among the farming countries. This statistical classification could be one of the useful tools to discriminate Japanese Koshihikari rice samples from the same species of rice samples farmed in the other countries. Therefore, stable isotope ratios of light elements, such as H, C, N, and O, in food samples (e.g., rice, beef, and eel) were precisely analyzed. The results may be explained by the regional differences in the isotope signatures of the climate, utilized nutrition, and/or quality of irrigation water among the farming countries. Stable isotopic traceability could thus be useful to extract food samples (fruit, rice, meat, fish, etc.) grown in Japan from those in the rest of the world. Dynamics analysis studies on stable isotopic behavior (i.e., isotopomics) in metabolism may be looking forward to establish a new science.
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Technical Papers
  • Noriya MASAMURA, Ryo KIKUCHI, Yasuaki NAGATOMI
    Article type: Technical Papers
    2014 Volume 63 Issue 3 Pages 245-253
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    We developed a method to identify plant materials by amplifying by PCR the internal transcribed spacer 1 (ITS 1) region located between the 18S ribosomal RNA (18S rRNA) and the 5.8S ribosomal RNA (5.8S rRNA) genes using plant universal primers designed on the two genes, and determining the nucleotide sequence of the amplified product. The primer designed on the 18S rRNA gene is universal to a wide range of plant species, designed from a nucleotide sequence not found in fungi or yeast, and thus is applicable to plant materials contaminated with fungi/yeast. The current method correctly identified 36 of 45 commercially available plant species, including 9 plants identified up to the genus level. Onion scale leaves heated at 105°C for 16 hrs and onion scale leaves contained in retort sauce were also identified. The method was then tested for itsability to identify possible contaminants in food, including peanut seed coat, calyxes of apples and pumpkins, bamboo, wood pieces and the pericarp of frozen eggplants. PCR products were obtained from the peanut, pumpkin and apple materials, and these plants were identified up to the species or genus level. These results suggest the potential of the current method for identifying plant contaminants in food.
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  • Yoshiki ISHIDA, Kenji NAKAMURA, Kaoru ARIYAMA, Akira KAWASAKI
    Article type: Technical Papers
    2014 Volume 63 Issue 3 Pages 255-261
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    We developed an identification method concerning the geographic origin of wheat grain based on its trace element concentrations and heavy element isotopic ratios by means of high-resolution inductively coupled plasma mass spectrometry. Wheat samples collected from three origins (Australia, North America and Japan) were characterized by 9 parameters (concentrations of Rb, Sr, Mo, Ba, Mn, Co, Zn and Se, and 87Sr/86Sr). In addition, eastern or western Australian wheat and the others could be accurately identified by 4 parameters (concentrations of Rb, Sr and Ba, and 87Sr/86Sr) regardless of the production year.
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Notes
  • Kyoko KAMATA, Tomoko HITOMI, Yasushi SEKIYAMA, Yuichi MIZUKAMI, Yuko W ...
    Article type: Notes
    2014 Volume 63 Issue 3 Pages 263-267
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    Allyl isothiocyanate (AITC) has been widely used in the food industry for its specific pungent odor and antibacterial effect. In this study, we measured stable carbon and nitrogen isotopic compositions of AITC by elemental analysis/isotope ratio mass spectrometry (EA/IRMS) in order to evaluate their potential as a conventional tool for discrimination between natural (i.e., plant-derived) and artificial products. A significant difference in the isotopic compositions for carbon (2–4‰) and nitrogen (22–30‰) was obtained between natural (N = 4) and artificial products (N = 2), which implies that isotopic analysis is potentially useful to discrimination natural and artificial AITCs, even though the number of examined samples is still small at this moment. We also demonstrated the carbon isotope analysis of AITC painted on plastic sheets by gas chromatography/isotope ratio mass spectrometry (GC/IRMS), which may suggest that isotope analysis is applicable to not only pure AITCs, but also to those found in complex mixtures as various industrial products.
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Analytical Reports
  • Hitomi S. KIKKAWA, Ritsuko SUGITA, Yasuo SETO
    Article type: Analytical Reports
    2014 Volume 63 Issue 3 Pages 269-273
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    Recently, many studies have attempted to discriminate and identify forensic botanical samples by DNA analysis. In this study, DNA was extracted from 4 plant species by 4 commercially available kits. Also, whether the purified DNA could provide sufficient quality for PCR amplification was examined. PCR of the rbcL partial region sequence, which is used as markers for phylogenetic and taxonomic studies, was performed after DNA extraction. Amplicon was observed from all of the samples extracted by DNeasy Plant Mini Kit, but not all samples by ISOPLANT and ISOPLANT II, and none of the samples by Genomic-tip. These results suggested that the amounts of the extracted DNA or PCR inhibitor differed depending on sample species and extraction kits. In addition, DNA from different parts of the plant body, such as flower, stem, root and seed, could be extracted using DNeasy Plant Mini Kit, and the rbcL partial region was successfully amplified by PCR. Therefore, the DNeasy Plant Mini Kit was considered to be suitable for DNA analysis of plant samples.
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  • Yaeko SUZUKI, Maya ISSHIKI, Rie SATO, Rumiko NAKASHITA
    Article type: Analytical Reports
    2014 Volume 63 Issue 3 Pages 275-278
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    In previous studies, stable carbon, nitrogen and oxygen isotope analyses were probably a useful tool for tracing the geographical origin of processed eels. However, the lack of a reliable technique for isotope ratio measurements is significantly regrettable, and should be improved immediately. Here, we present results of an inter-laboratory test on the EA-IRMS determination of stable carbon, nitrogen and oxygen isotopic compositions (δ13C, δ15N and δ18O) in processed eel samples. The processed eel samples were distributed and analyzed by a total of 5 laboratories. The variations of the standard deviations for δ13C (− 18.7‰ ± 0.2‰) and δ15N (+ 13.4‰ ± 0.3‰) among laboratories were not very large compared to the instrument uncertainties. The δ18O values (+ 16.5‰ ± 3.1‰) in processed eel samples showed a large variation among laboratories. This may have been caused by much the contamination of N2 to the CO peak on the EA-IRMS chromatogram, and may be improved by using a longer GC column or Purge & trap columns for chromatographic separation.
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  • Kyoko KAMATA, Yoshito CHIKARAISHI
    Article type: Analytical Reports
    2014 Volume 63 Issue 3 Pages 279-282
    Published: March 05, 2014
    Released on J-STAGE: March 31, 2014
    JOURNAL FREE ACCESS
    Compound-specific stable isotope analysis (CSIA) of nitrogenous compounds has been carried out by using a gas chromatography/isotope ratio mass spectrometry (GC/IRMS) system, which traditionally includes two separate conversion processes: the oxidation of nitrogenous compounds to N2 and NOX; and the reduction of the NOX to N2. However, the last major update of the GC/IRMS instrument combined these two processes into one unit by introducing a high-temperature combustion reactor. However, few studies have evaluated the applicability of this new GC/IRMS system to measuring the nitrogen isotopic composition of compounds of interest. In the present study, we determined the nitrogen isotopic composition of ten amino acids by this new GC/IRMS system, and obtained the isotopic composition with 0.6‰ for accuracy (mean of Δ) and 1.2‰ for precision (mean of 1σ). These results suggest that the new GC/IRMS system is basically applicable to the CSIA of nitrogenous compounds, and also that further optimization is required for reducing the analytical error to that of the traditional GC/IRMS system (ca. 0.0‰ for accuracy and 0.4–0.7‰ for precision).
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