Vol. 4 8, No. 1 0
October, 1999
Daisuke Umeno and Mizuo Maeda*
*Department of Materials Physics and Chemistry, Graduate School of Engineering, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka 812-8581
(Received 13 January 1999)The recent developments of affinity techniques concerning single- and double-stranded DNA are reviewed. Based on the opinion that the immobilization of DNA is essential for the analytical and preparative use of the ligand function of DNAs, the two items are extensively discussed concerning the choice of conjugation chemistry and supports. Finally, a variety of applications, mainly for sensing and purification, are discussed.
Keywords : affinity separation; biosensor; hybrid material; bioconjugate; immobilized DNA; DNA-binding protein; DNA chip.
Akinori Isozaki, Hiroto Shimamura, Satoshi Takeda*, Hisomu Nagashima** and Tadao Okutani*
*Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-ku, Tokyo 101-8308
**Institute of Science and Technology, Inc., 3-10-2, Kitashinagawa, Shinagawa-ku, Tokyo 140-0001
A new method for the determination of trace amounts of bromate ion has been developed for ion chromatography with suppressed conductivity detection and a graphitized carbon column. A 2 mM sodium carbonate solution containing 1 mM tetrabutylammonium hydroxide (TBA-OH) in 1% acetonitrile was used as an optimal mobile phase for the simultaneous determination of a mixture of seven anions (F-, Cl-, NO2-, BrO3-, Br-, NO3- and SO42-). The seven anions were efficiently separated within 20 minutes, and the bromate ion was eluted after the nitrite ion was separated from the chloride ion. The calibration curve of the bromate ion was linear with excellent correlation coefficients of more than 0.999, and the relative standard deviation of the peak areas was 0.80% from five repeated measurements at 100 µg/l; the limit of detection was 1 µg/l. When a high concentration of chloride ion was present in sample solution, it was passed through a Ag cartridge. This method was applied to the determination of bromate ion in water samples, such as tap water, mineral water and river water.
Keywords : bromate; ion chromatography; graphitized carbon column; tetrabutylammonium.
Shan Ji, Tomoki Yabutani, Fumihiko Mouri, Chisen Kimata, Akihide Itoh, Koichi Chiba and Hiroki Haraguchi*
*Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603
(Received 6 May 1999, Accepted 17 July 1999)The multielement determination of major-to-trace elements in insoluble particulates of solar salt was carried out by ICP-AES and ICP-MS. A solar salt sample (30 g) was dissolved in 1 l of pure water to adjust its solution salinity to be almost the same as that of seawater. When the solar salt sample solution was filtered using a membrane filter (pore size 0.45 µm), the residue on the filter was defined as the insoluble particulates and the filtrate as the soluble constituents. The insoluble particulates were decomposed together with the membrane filter by an acid digestion method using HNO3, HF, and HClO4. As a result, 36 elements in the insoluble particulates could be determined at % to sub-µg g-1 levels by ICP-AES and ICP-MS. Taking into consideration the present results along with the analytical results for the soluble constituents reported in a previous paper, alkali elements, alkaline earth elements, Mo and Cd were found mainly in the soluble constituents of solar salt, while Al, Ti, V, Fe, Co, Ga, Y, Sn, and rare-earth elements (REEs) were found in the insoluble particulates. Iron, Co, Y, Sn, and REEs in the insoluble particulates were partly leached into the acid solution when the solar salt sample was dissolved in a 0.1 M HNO3 solution. Thus, it is considered that these elements are dissolved as colloidal matter adsorbed on particulates in seawater. On the other hand, because Mn, Cu, Zn, and Pb were found in both the insoluble particulates and the soluble constituents, these elements in the insoluble particulates were easily leached in a 0.1 M HNO3 solution. These results indicate that Mn, Cu, Zn, and Pb are contained as acid-soluble forms in the insoluble particulates. Moreover, the relative abundances of the elements normalized to the Al concentrations in the insoluble particulates of solar salt and the marine sediment standard material (NIES No. 12) showed a good linear correlation, which suggests that the insoluble particulates in solar salt are an origin of marine sediment.
Keywords : solar salt; insoluble particulate; multielement analysis; ICP-AES; ICP-MS.
Tatsunari Yoshida, Tadashi Okada* and Toshiyuki Hobo**
*Analytical Laboratory, Nanyo Research Center, Tosoh Corporation, 4560, Kaisei-cho, Shinnanyo-shi, Yamaguchi 746-8501
**Department of Applied Chemistry, Graduate School of Engineering, Tokyo Metropolitan University, 1-1, Minami-Ohsawa, Hachioji-shi, Tokyo 192-0397
An experimental procedure for peptide separation by normal-phase liquid chromatography (NPLC) was proposed in previous papers. In the present study, the chromatographic behavior of amino, cyano, amide, diol and silica columns, which have been used in non-aqueous NPLC, was newly investigated. The amino column was not appropriate for this peptide separation because of poor recovery. The cyano column could not be used due to a lack of retention. The amide, diol and silica columns were useful for peptide separation. The chromatograms on amide, diol and silica columns were slightly different when the mobile-phase composition was changed. Furthermore, the relationship between the retention time and the amount of modifier in the mobile phase was investigated with each column. There was a linear relationship between the logarithm of the retention factor and the logarithm of the modifier ratio in each column.
Keywords : peptide; stationary phases; mobile phase composition; selectivity; retention factor.
Tatsunari Yoshida, Tadashi Okada* and Toshiyuki Hobo**
*Analytical Laboratory, Nanyo Research Center, Tosoh Corporation, 4560, Kaisei-cho, Shinnanyo-shi, Yamaguchi 746-8501
**Department of Applied Chemistry, Graduate School of Enginnering, Tokyo Metropolitan University, 1-1, Minami-Ohsawa, Hachioji-shi, Tokyo 192-0397
It was reported in a previous paper that the separation of peptides took place in normal-phase liquid chromatography on amide, diol and silica columns. In this study, the contribution of individual amino acid residues to the retention of peptides was evaluated in order to clarify the mechanism of peptide separation. This paper lists the "hydrophilicity retention coefficients". The retentions of 121 peptides were measured through normal-phase liquid chromatography on the amide, diol and silica columns using an acetonitrile-water mixed solution containing 0.2% trifluoroacetic acid + 0.2% triethylamine as the mobile phase in a linear gradient elution system. For the silica column, the best-fit hydrophilicity retention coefficients could be calculated by a linear-regression analysis. For the amide and diol columns, the best-fit hydrophilicity retention coefficients could be calculated by a non-linear regression analysis. A set of the hydrophilicity retention coefficients on each column successfully explained the contribution degree of retention on each column.
Keywords : peptide; selectivity; stationary phases; hydrophilicity; retention.
Toshimitsu Okamoto*, Akinori Isozaki, Tadao Okutani** and Hisomu Nagashima***
*Product Development Laboratories, Sankyo Co., Ltd., 1-2-58, Hiromachi, Shinagawa-ku, Tokyo 140-8710
**Department of Industrial Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-ku, Tokyo 101-8308
***Institute of Science and Technology, Inc., 3-10-2, Kitashinagawa, Shinagawa-ku Tokyo 140-0001
A graphitized carbon column for ion chromatography has been used in the simultaneous determination of inorganic anions in various samples. This paper describes an investigation on the durability of column using color additives for drugs and cosmetics (D&C colors) as an injection matrix. The effects of the matrix on the retention behavior were examined for 6 common anions (F-, Cl-, NO2-, Br-, NO3- and SO42-) after 10 repeated injections of an aqueous solution of 1.0 mg ml-1 Acid Yellow 1. The number of theoretical plates and peak areas for anions after 90 injection were in good agreement with those at initial injection, while avoiding any matrix effect. In addition, simultaneous determination of chloride, bromide and sulfate in D&C colors was examined after a pretreatment for the selective removal of D&C colors. A Sep-Pak C18 cartridge as a chemical filter and 0.05 mM tetrabutylammonium (TBA) in a sample solvent were effective to retain the D&C colors, while chloride, bromide and sulfate passed through unretained. The recoveries of Cl- (7.5), Br- (1.5) and SO42- (1.5 µg ml-1) added to six D&C colors (0.1 mg ml-1) were 99.8~101.2%, 98.3~99.7% and 95.1~97.5%, respectively.
Keywords : tetrabutylammonium; chloride; bromide; sulfate; color additives;chemical filter.
Sachiyo Nakagawa, Itsuo Mori, Takako Matuo, Yasuyuki Shigemura and Yoshikazu Fujita*
*Osaka University of Pharmaceutical Sciences, 4-20-1, Nasahara, Takatsuki-shi, Osaka 569-1024
(Recieved 4 June 1999, Accepted 17 July 1999)A spectrophotometric method for the determination of chlorpheniramine maleate(CPM) was established by using Bromopyrogallol Red(BPR) and niobium(V). This method can be used to determine 2~32 µg/10 ml CPM at 635 nm. The apparent molar absorptivity is 8.0×104 l mol-1 cm-1 with a relative standard deviation (n = 8, 19.6 µg) of 0.83%. The proposed method, which is a simple procedure without separation, was applied to assays of CPM in pharmaceutical preparations (eye drop, syrup, capsule and lotion). The analytical results and recoveries were satisfactory.
Keywords : chlorpheniramine maleate; spectrophotometry; pharmaceutical preparations; Bromopyrogallol Red and niobium(V).
Akiko Tanabe*, Shigeru Suzuki** and Yoshifumi Hanada***
*Niigata Prefectural Research Laboratory for Health and Environment, 314-1, Sowa, Niigata 950-2144
**Research Institute for Environmental Protection City of Kawasaki, 20-2, Tajima-cho, Kawasaki-ku, Kawasaki-shi 210-0853
***Kitakyushu City Institute of Environmental Sciences, 1-2-1, Shinike, Tobata-ku, Kitakyushu-shi, Fukuoka 804-0082
An ultrasonic extraction method was evaluated for a GC/MS determination of polyaromatic hydrocarbons (PAHs) and n-alkanes in airborne particulate matter, compared with the Soxhelet extraction method. Three airborne particulate samples collected at an industrial area of Kitakyushu City, a heavy traffic area of Kawasaki City, and Urban Dust (Standard Reference Material 1649) were extracted for seven PAHs and eight n-alkanes by both the ultrasonic extraction method with cyclohexane-ethanol (3:1) and Soxhelet extraction method with benzene-ethanol (3:1). Vehicle Exhaust Particulate (NIES No. 8) was also extracted for the compounds by the two methods. The results of the target compounds by the ultrasonic extraction method well agreed with those by the Soxhelet extraction method, except for the vehicle exhaust particulate.
Keywords : polyaromatic hydrocarbon; n-alkane; GC/MS; ultrasonic extraction; airborne particulate matter.
Hajime Goto, Jin-Ming Lin and Masaaki Yamada*
*Department of Industrial Chemistry, Faculty of Engineering, Tokyo Metropolitan University, 1-1, Minami-ohsawa, Hachioji-shi, Tokyo 192-0397
(Received 22 June 1999, Accepted 13 July 1999)An isoluminol chemiluminescent(CL) reactin on bariumperoxide (BaO2) was applied for the detection of bile acids after high performance liquid chromatographic (HPLC) separation. N-(4-Aminobutyl)-N-ethylisoluminol (ABEI) was used as a pre-labelling reagent for bile acids. In the proposed CL detection system, no CL reagents were required, because superoxide existed on the basic surface of BaO2. Ursodeoxycholic acid was detected at levels as low as 10 pmol, more sensitive than that in HPLC-UV methods.
Keywords : bariumperoxide; chemiluminescence detection; HPLC; bile acid.
Tohru Yamagaki
National Institute of Bioscience & Human-Technology, AIST, 1-1 Higashi, Tsukuba, Ibaraki 305-8566
Awarded by Saitama University dated March 25, 1999Structural analyses of carbohydrates were performed by a new technique using MALDI-TOF mass spectrometry. Sequential fragment ions were observed in the post-source decay (PSD) fragment spectra of MALDI-TOFMS, which are like the MS/MS fragment spectra. These fragment ions were produced by cleavages of the glycosidic linkages. The structural isomers of sugar-branched cyclodextrin derivatives were distinguished by a relative ion intensity analysis. The fragment ions produced by one-site cleavage of the glycosidic linkage had a much higher intensity than that produced by two-site cleavage. In addition, the glycosidic linkage of α1-4 cleaved more easily than that of α1-6 in MALDI-PSD fragmentation. These results strongly indicated that the relative ion intensity analyses of these MALDI-PSD fragment ions enable us to distinguish structural isomers and to perform a linkage analysis.
(Received July 2, 1999)Keywords : MALDI-TOFMS; post-source decay (PSD); carbohydrate; isomers; linkage analysis.
Susumu Shimoyama
Color Material Research Laboratory, Den Material Co., Ltd., 5396, Kamiogino, Atugi-shi, Kanagawa 243-0201
Awarded by Iwaki Meisei University, dated March 22, 1998For the purpose of the title, the fluorescence spectra of dyestuffs were measured with a Hitachi F-4500 spectrophotometer equipped with a personal computer for data transaction and a double-bundle-type fiber-optic cable. Three-dimensional (3-D) spectra were drawn as contour plot diagrams of the fluorescence intensity upon the coordinate of excitation vs emission wavelength. The 3-D spectra of standard natural dyestuffs (fifteen botanical and one mollusc origins) dyed on silk and/or cotton (for cloths) and Japanese paper (for Ukiyo-e) could be distinguished from the position of the top ring of contour lines and their fingerprint patterns, even though it contains two or three main components. From a comparison of the 3-D spectrum with standards, the origin of the colored textile remnant attached on a shell bracelet found at Yoshinogari ruin (B.C. 100) was identified to be deteriorated Tyrian purple, and blue, green, red yarns interwoven into Chinese Brocade (A.D. 1600~1700) to be indigo, Amur cork and indigo, Amur cork and safflower, respectively. Concerning Ukiyo-e, red and yellow colors on "Yokkaichi" from fifty-three-stages of Tokaido (A.D. 1823) by Katsushika Hokusai, and blue color on "Evening Snow" from eight views of Edo (A.D. 1821) by Gototei Kunisada were determined to be safflower, turmeric and indigo, respectively.
(Received July 13, 1999)Keywords : non-destructive determination; natural dyestuffs; ancient colored cloths; ukiyo-e prints; three-dimensional fluorescence spectra.
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