BUNSEKI KAGAKU Abstracts

Vol. 53 No. 3

March, 2004


Reviews

Biosensing technology for cellular and tissular responses

Shinya Ikeno1,2 and Tetsuya Haruyama1,2

1 Department of Biological Functions and Engineering, Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, Kitakyushu Science and Research Park, 2-4, Hibikino, Wakamatsu-ku, Kitakyushu-shi, Fukuoka 808-0196
2 CREST, Japan Science and Technology Agency, 4-1-8, Honcho, Kawaguchi-shi, Saitama, 332-0012

(Received 4 November 2003, Accepted 14 January 2004)

Cells correspond to the minimum functional unit in the organism living system and respond first to the chemical and physical stimulus. Such signals might be useful as parameters for recognition of living system status which is damaged by various factors, and the detection will be applicative for chemical information for its safety, drug efficacy profile. However, such cellular signals are very week and intractable detected using conventional analytical methods. Recently, developments of technology such as nanotechnology, molecular designing, genetic engineering, cellular and tissue engineering etc., have been brought the great contribution for life science such as research of medicine, molecular biology. Bioimaging using fluorescence probes are enable to easily visible detection for cellular and tissular function, and more functional cells translated by gene cloning technology have brought to sharply extend the possibility of cellular biosensing. Using new technology of biosensor, cellular and tissular function have been detected in situ. This review paper includes cellular biosensing technologies response to either toxic compounds or chemicals being considered for a medicinal drug for humans.

Keywords : bioimaging; biosensor; cellular responses.


Research Papers

Determination of trace impurities in high-purity zirconium oxide by high-resolution inductively coupled plasma mass spectrometry

Kiyoshi Nakane1

1 National Institute of Advanced Industrial Science and Technology (AIST), Ceramics Research Institute, 2266-98, Anagahora, Shimoshidami, Moriyana, Nagoya-shi, Aichi 463-8560

(Received 14 March 2003, Accepted 11 December 2003)

Using high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS), trace impurities in high-purity zirconium oxide powder samples were determined. A 0.5 g zirconium oxide sample was dissolved with 5 ml of sulfuric acid (1+1) in a PTFE pressure vessel at 230°C for 40 h. Most of the spectral interferences were avoided by using a high-resolution spectrometer. The matrix effects of Zr were investigated. Since the matrix effects of a high Zr concentration on the peaks of the internal standard were similar to those on almost all of the analyte elements, except for Hf, the internal-standard method was employed for quantitative analysis. Indium was used for the internal standard element. The analytical values, except for Hf obtained by the internal-standard method, approximately agreed with those obtained by the standard addition method. The analytical values of the Hf obtained by ICP-AES approximately agreed with those obtained by the standard addition method. The detection limits in the solid samples were in the range of 0.01~9 µg g-1. The determinations for Na, Mg, Al, Ca, Ti, V, Cr, Mn, Fe, Ni, Sr, Cs, La, Ce, Hf, Pb and Bi in three kinds of commercially available high-purity zirconium oxide powders are presented.

Keywords : high-resolution inductively coupled plasma mass spectrometry; high-purity zirconium oxide; matrix effects; internal standard method.


On-site analysis of Islamic glass excavated in the Sinai Peninsula by a portable X-ray fluorescence spectrometer for classification of glasses based on their chemical compositions

Takashi Sawada1, Akiko Hokura1, Shoko Yamada1, Izumi Nakai1 and Yoko Shindo2

1 Faculty of Science, Tokyo University of Science, 1-3, Kagurazaka, Shinjuku-ku, Tokyo 162-8601
2 The Middle Eastern Culture Center in Japan, 3-10-31, Osawa, Mitaka-shi, Tokyo 181-0015

(Received 30 June 2003, Accepted 21 December 2003)

Glass samples (8th~12th century A.D.) excavated from archaeological sites (Raya and Wadi al-Tur) of Islamic periods in the Sinai Peninsula of Egypt were analyzed in situ by a portable XRF spectrometer developed by our group. It was found that the content of Mn, Br, Sr, and Pb was useful to classify the non-decorated glass fragments. A total of 223 fragments of Islamic glass could be classified into the natron glasses (n=127) and plant ash glasses (n=96) based on their SrO vs. K/Ca plots. It is suggested that the content of Sr can be used instead of Mg in classifying Islamic glasses. In addition, it was found that TiO2 vs. SrO plot was also useful for classifying Islamic glasses.

Keywords : portable XRF; Islamic glass; archeological analysis; field analysis; chemical composition.


Technical Papers

Application of 2-(2,3-naphthalimino)ethyl trifluoromethanesulphonate as a pre-column derivatization reagent for high-performance liquid chromatography in the determination of 3-hydroxybutyrate in aqueous solution

Rie Nakahara1, Katsushi Inamura2, Gen Watanabe2, Shin Ohta3, Kenji Shimada1 and Susumu Yamato1

1 Department of Analytical Chemistry, Faculty of Pharmaceutical Sciences, Niigata University of Pharmacy and Applied Life Sciences, 5-13-2, Kamishin'ei-cho, Niigata-shi, Niigata 950-2081
2 Department of Pharmacy, Toyama Rousai Hospital, 992, Rokuro-maru, Uodu-shi, Toyama 937-0042
3 Department of Pharmacy, Nagano Red Cross Hospital, 5-22-1, Wakasato, Nagano-shi, Nagano 380-8582

(Received 15 October 2003, Accepted 8 January 2004)

2-(2,3-Naphthalimino)ethyl trifluoromethanesulphonate (NE-OTf), as a pre-column derivatization reagent for high-performance liquid chromatography, has been tried for the determination of 3-hydroxybutyrate in aqueous solution. Thus far, NE-OTf has been inapplicable to short-chain carboxylic acids and an aqueous reaction system. 3-Hydroxybutyrate in aqueous solution reacted completely with an excess amount of NE-OTf in the presence of dimethyl sulfoxide, and N-ethyldiisopropylamine under a water-bath with sonic vibration setted at 45°C for 40 min. Under this condition, excess amounts of NE-OTf were also completely destroyed, and any chromatographic peaks due to by-products did not interfere with the determination of 3-hydroxybutyric acid ester derivative. The calibration curve of a 3-hydroxybutyrate standard solution was linear over the range of 0.02~2.0 nmol for 10 µl injection, with a correlation coefficient of 0.9988. The detection limit (signal-to-noise ratio=3) for 3-hydroxybutyrate was 2 pmol for 10 µl injection. By this method, NE-OTf was successfully applied to the determination of 3-hydroxybutyrate in aqueous solution.

Keywords : HPLC; UV detection; derivatization; 3-hydroxybutyric acid; 2-(2,3-Naphthalimino)ethyl trifluoromethanesulphonate.


Notes

Correlation coefficients between biomarkers and sub-surface microbial activities in terrestrial sediment over the past 10000 years

Yoshinori Takano1, Takeo Kaneko2, Kensei Kobayashi2 and Katsumi Marumo1

1 Institute for Marine Resources and Environment, National Institute of Advanced Industrial Science and Technology (AIST), AIST Central 7, 1-1-1, Higashi, Tsukuba-shi, Ibaraki 305-8567
2 Department of Chemistry and Biotechnology, Yokohama National University, 79-5, Tokiwadai, Hodogaya-ku, Yokohama-shi, Kanagawa 240-8501

(Received 11 November 2003, Accepted 15 January 2004)

Core samples of terrestrial sediments at depths of 0~300 cm at Rikubetsu, Hokkaido, Japan were analyzed for determining the product moment correlation coefficient (r) regarding amino acids, amino sugars, total organic carbon, total sulfur, enzymatic activities and microbial cell density. The abundance of sedimentary organic matter and the density of viable microorganisms were greatest at the surface, and drastically decreased with the depth. However, the D/L ratio of chiral amino acids and non-proteinous amino acids, such as β-alanine and γ-aminobutyric acid, showed a negative correlation with the depth. Hence, racemization reactions and the alteration of dicarboxylic amino acids, aspartic acid and glutamic acid, to β-alanine and γ-aminobutyric acid, respectively, via specific decarboxylation due to diagenesis were observed over the past 10000 years. The vertical distributions of biomarkers are highly consistent with the subterranean microbial activities in the sediment.

Keywords : diagenesis; organic matter; microbial activity; correlation coefficient.


Determination of calcium in natural water samples by atomic absorption spectrometry by adding reduced amounts of lanthanum chloride

Masayoshi Koga1, Masashi Nishida1 and Isao Yoshida1

1 Department of Applied Chemistry, Faculty of Engineering, Sojo University, 4-22-1, Ikeda, Kumamoto-shi, Kumamoto 860-0082

(Received 25 November 2003, Accepted 18 January 2004)

The concentrations of calcium in river and underground water samples of Kikuchi River and Kikusui-machi in the northern area of Kumamoto Prefecture and in two commercially available drinking water samples, Volvic and Morinomizudayori, were measured by suppressing interference due to coexisting components, such as aluminum, silicate, sulfate and phosphate ions, by adding a smaller amount of lanthanum chloride than that indicated in the JIS method, 2×103 ppm. The calcium concentrations measured in the presence of 30 to 50 ppm lanthanum almost agreed with those by chelatemetric titration(EDTA) and inductively coupled plasma atomic emission spectrometry(ICP-AES). The proposed AAS with an acetylene-air flame is a facile and environmentally protective method for the determination of calcium in natural water samples.

Keywords : calcium concentration; natural water; AAS; suppression with reduced lanthanum chloride.


Technical Letters

International comparison on the determination of polychlorinated biphenyl congeners in sediment

Takashi Yarita1, Atsuko Nakama1, Kazuko Yoshimura1, Akiko Takatsu1 and Kensaku Okamoto1

1 National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 3-10, 1-1-1, Umezono, Tsukuba-shi, Ibaraki 305-8563

(Received 20 October 2003, Accepted 23 December 2003)

An international comparison (CCQM-P17) on the determination of polychlorinated biphenyl (PCB) congeners in sediment by national metrology institutes was carried out. We participated in this comparison by applying pressurized fluid extraction (PFE), followed by isotope-dilution gas chromatography/mass spectrometry (ID-GC/MS). Details of our results for the determination of the four target congeners are described in terms of a quantification procedure using an equation that has been used for describing the IDMS method, a comparison of the PFE efficiency with that by Soxhlet extraction, and an evaluation of the uncertainties of the measurement. Full results of the international comparison are also given, in which our results are comparable to those reported by a majority of the participants.

Keywords : international comparison (CCQM-P17); polychlorinated biphenyls; sediment; isotope-dilution mass spectrometry; pressurized fluid extraction.


Portable X-ray fluorescence spectrometer with an electric battery

Jun Kawai1, Takashi Yamada2 and Hajime Fujimura3

1 Department of Materials Science and Engineering, Kyoto University, Sakyo-ku, Kyoto-shi, Kyoto 606-8501
2 Rigaku Industrial Corporation, 14-8, Akaoji, Takatsuki-shi, Osaka 569-1146
3 Rigaku Corporation, 14-8, Akaoji, Takatsuki-shi, Osaka 569-1146

(Received 21 November 2003, Accepted 24 December 2003)

Keywords : X-ray fluorescence; Cd; Pb; portable spectrometer; dry electric battery.


Digests of Doctoral Dissertation

Synthesis of novel solid materials for the separation of metals by derivatizing biomass with functional moieties and their application to analytical chemistry

Koji Oshita

3-1-1, Tsushimanaka, Okayama-shi, Okayama 700-8530

(Awarded by Okayama University dated March 25, 2003)

A cross-linked chitosan (CLC) was newly synthesized with ethylene glycol diglycidyl ether (EGDE). Novel chelating resins, possessing IDA (IDA-CLC), IDP (IDP-CLC), glycine (glycine-CLC), valine (valine-CLC), leucine (leucine-CLC) and serine (serine-CLC) moieties, were synthesized, and were applied to the collection and concentration of trace metals in environmental water samples. The adsorption of metal ions at 10 ng ml-1 levels on chelating chitosan resins was studied by a column-treatment. Synthesized chitosan resins are specific for each moiety as follows: CLC for the collection of Hg(II) in conc. HCl solution; IDA-CLC for matrix elimination and multi-elements collection; IDP-CLC for the separation of rare earth elements (REEs); glycine-CLC for the collection of Bi(III); leucine-CLC for the collection of Mo(VI); and serine-CLC for the collection of U(VI). The synthesized resins could be used for the preconcentration of these elements in environmental water samples by column operation prior to determination by ICP-MS, ICP-AES and GFAAS.

(Received October 30, 2003)

Keywords : cross-linked chitosan; chelating resin; ion exchange resin; collection; concentration; separation; ICP-MS; ICP-AES; GFAAS.


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