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Volume 53, Issue 7
Displaying 1-15 of 15 articles from this issue
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Review
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Takeshi OHNO, Takafumi HIRATA2004 Volume 53 Issue 7 Pages 631-644
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSMass spectrometers utilizing an atmospheric pressure inductively coupled plasma (ICP) as an ion source have been widely used for elemental and isotopic analyses of trace elements in various samples. The strength of ICP-mass spectrometer (ICP-MS) lies with the ion source that achieves high ionization efficiency for almost all elements. An extension of the capability of ICP-MS is to accept dry samples generated by a laser ablation technique (LA). The combination of LA and ICP-MS techniques has opened up a completely new field of the Earth science for which spatial resolution is required. Recently, the measurement of isotopic ratios by multiple collector-ICP-MS (MC-ICP-MS) has been described. The precision of isotopic ratios achieved by the MC-ICP-MS technique is comparable to those exhibited by the TIMS technique. Precise isotopic data obtained by the MC-ICP-MS technique have revealed that natural stable isotope fractionations of many elements heavier than S (e.g., Fe, Cu, Zn) are common on the Earth. In this paper, we review recent outstanding studies on isotope geochemistry achieved by LA-ICP-MS and MC-ICP-MS techniques.
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Account
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Tatsuya HIGASHI, Kazutake SHIMADA2004 Volume 53 Issue 7 Pages 645-655
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSSteroids are essential bio-molecules for the maintenance of life. Kinetic and functional analyses of steroids are necessary to elucidate the nature of the many endocrine disease processes, and thus be useful for diagnosis and treatment. High-performance liquid chromatography/mass spectrometry (LC/MS) has recently been used for steroid analysis due to its specificity and versatility. However, conventional LC/MS sometimes does not demonstrate the required sensitivity for the trace analysis of steroids in biological samples, because the ionization efficiencies of most steroids are relatively low for electrospray ionization and usual atmospheric pressure chemical ionization (APCI). On the other hand, electron-affinitive compounds are efficiently ionized by the electron capture reaction in APCI in the negative-ion mode (electron capture APCI). Therefore, in this mode, a high sensitivity can be obtained by tagging steroids with electron-affinitive (electron capturing) moieties. On this basis, we have developed detection-oriented derivatization methods for the LC/electron capture APCI-MS analysis of steroids and applied these methods to the determination of vitamin D3 metabolites in human plasma and to the analysis of changes in rat brain neurosteroid levels by acute stress.
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Takashi ITO2004 Volume 53 Issue 7 Pages 657-675
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThis account describes recent studies preformed by the author and his coworkers regarding new analytical methodologies based on chemical and steric interactions at liquid-liquid interfaces, at solid-liquid interfaces and within nanopores. These studies aim at (1) experimental and theoretical understanding of potentiometric responses to uncharged phenols observed with PVC-supported liquid membranes, (2) electrochemical sensing of trivalent lanthanoid ions using chelating ligands at liquid-liquid and solid-liquid interfaces, (3) force-based chemical sensing using chemically-modified atomic force microscopy (AFM) tips, (4) discrimination of surface molecules and functional groups using molecular scanning tunneling microscopy (STM) tips, and (5) single nanoparticle/molecule detection and discrimination using single MWNT channels. These methodologies provide a means for obtaining unique molecular/nanoparticle information as well as for developing new chemical sensors. In addition, some of them can detect and discriminate single molecules and nanoparticles, and thus permit us to develop not only new highly-sensitive, absolute analytical methods but also to develop new analytical techniques that provide both the average and intrinsic distribution of analyte properties.
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Kenji HAMASE, Kiyoshi ZAITSU2004 Volume 53 Issue 7 Pages 677-690
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSSensitive and selective methods for the determination of small amounts of D-amino acids in mammalian tissues have been established using a two-step HPLC system with a reversed-phase column and a chiral column. A chiral derivatization method using o-phthalaldehyde and N-tert-butyloxycarbonyl-L-cysteine has also been reported for the simultaneous reversed-phase HPLC separation of D-aspartic acid, D-serine and D-alanine. Using these methods, the distribution and alteration of the amounts of D-alanine, D-leucine and D-proline in mammals have been clarified for the first time, and compared with those of D-aspartic acid and D-serine, which have already been reported for several mammalian tissues. The amounts of D-alanine, D-leucine and D-proline are much smaller than those of D-aspartic acid and D-serine, and the values are less than 1% of that of the L-form in most tissues. The amounts of D-alanine have been determined in 22 tissues of rats including the central nervous system and the periphery, and the highest value of 86.4 nmol/g wet tissue has been observed in the anterior pituitary gland. The amounts of D-alanine in this tissue increased until 6 weeks of age, and gradually decreased thereafter. The circadian changes of the D-alanine amounts in the anterior pituitary gland have also been revealed to show higher amounts during the light period. The distribution and alteration of the amounts of D-leucine and D-proline are totally different from those of D-alanine, indicating that these D-amino acids are strictly recognized in mammalian tissues.
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Research Paper
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Yuji SUZUKI2004 Volume 53 Issue 7 Pages 691-698
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThe dye-binding method based on the protein error of a pH indicator are classified into two groups: one is a methodology that records the absorbance increase in the reaction occurring at a lower pH range; the other is a methodology that records the absorbance decrease in the reaction occurring at a higher pH range. Because the procedure of the latter is somewhat troublesome compared with the former, the latter is almost not employed as the principle for determining serum protein. However, at present, with progress for an automatic analyzer, such a methodology whose procedure is somewhat troublesome is also able to be used as a principle for protein determination. Thus, since this methodology has so far only been examined a little experimentally, but not so much theoretically, the author investigated the characteristics of this methodology by means of a theoretical analysis based on the chemical equilibrium of the protein error observed in a reaction between the protein and a pH indicator, and compared these results with those obtained in an experiment using four sulfonphthalein pH indicators. In this methodology: 1) An absorbance decrease occurs in all dyes in a restricted pH range, and its magnitude changes by an equilibrium constant of the reaction, dye concentration, and molar absorptivities of the dye and the dye-protein complex. 2) The decreased absorbance observed in the reaction is proportional to the protein concentration; this phenomenon is applicable to the determination of serum albumin. 3) As the dye concentration increases, the calibration curve approaches a straight line. These calculated results agree well with the experimental results, indicating that the calculation described here is useful as a tool to examine the characteristics of the dye-binding method.
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Yohei USHIROZAWA, Hideyuki MATSUTA, Kazuaki WAGATSUMA2004 Volume 53 Issue 7 Pages 699-703
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThis paper describes a new excitation source for emission spectrometry consisting of an r.f. helium glow-discharge plasma and a laser-diode pumped Q-switched Nd : YAG laser. The Nd : YAG laser works dominantly as a sampling source for introducing of sample atoms into the helium glow-discharge plasma, because the laser-induced plasma, which may excite the sample atoms, cannot be produced by the laser itself due to its high repetition rate. On the other hand, the helium glow-discharge plasma mainly acts as an excitation source, because small amounts of the sample atoms can be introduced due to the low sputtering rate. However, the excited species of helium has the excitation capability for sample atoms requiring large excitation energies due to the high metastable levels. From these characteristics in this combined emission source, the sampling process and the excitation process could be controlled independently. Furthermore, it was possible to excite analyte elements having high excitation energies. In this paper, fluorine atomic lines requiring an excitation energy of about 14 eV were measured. These lines were detected only when the laser was irradiated to the helium plasma. The calibration curve for the FI 685.60-nm line gave a linear relationship in a LiF concentration range of 0.02∼5.0 mass%.
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Susumu ICHINOKI, Setsuko WATANABE, Saki MATSUIDA, Youichi FUJII, Toshi ...2004 Volume 53 Issue 7 Pages 705-713
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSCarbamate pesticides (pirimicarb, PHC, bendiocarb, XMC, NAC, ethiofencarb, and MIPC) in human serum and urine were determined by an automatic on-line column-enrichment technique followed by reversed-phase high-performance liquid chromatography with photometric detection. After human serum was filtered through a membrane filter (0.45 μm pore size), an aliquot of 0.1 ml of the filtrate was diluted with water up to 1 ml. A solution of 0.8 ml was directly injected to an automatic HPLC without any pretreatment. Human urine was incubated with β-glucuronidase/arylsulfatase for 16 hours at 37°C. The resultant solution was then filtered through a membrane filter and the filtrate was analyzed by a similar manner as the serum. Carbamates in the sample solution were concentrated on a pre-conditioned ODS mini-column. After washing the mini-column with 10% methanol, they were separated by an ODS analytical column (Cosmosil 5 C18-MS-II, 250×4.6 mm ID, 5°C) with an acetonitrile/water eluent (32 : 68, v/v) and detected at 220 nm. The presented HPLC method requires neither a manual procedure of solid-phase nor liquid-liquid extraction. Calibration curves for seven carbamates were linear over the range of 0.1∼50 μg/ml in serum, and 1∼50 μg/ml in urine. Recovery tests were carried out with human serum and urine. Recoveries of 25 and 2.5 μg in serum were 100∼103%, and those of urine were 98∼104%. The relative standard deviations of the recoveries were less than 3%.
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Taro UCHIDA, Ayumi YOSHIDA, Kanako TAKAHASHI, Seiichiro HIGUCHI2004 Volume 53 Issue 7 Pages 715-722
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThe curing and degradation of oil paint thin films exposed with air pollutant gas i.e. NO2 and SO2 were investigated in terms of the functional goup level by NIR-excited fourier transform Raman spectroscopy. It was shown that the actions of NO2 gas and SO2 gas for paint films were clearly different between NO2 and SO2 for oil paints containing the inorganic and the organic pigments.
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Toshio TAKAYANAGI, Rim DRIOUICH, Kuniko SAWAI, Qiong LI, Mitsuko OSHIM ...2004 Volume 53 Issue 7 Pages 723-728
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSSeparation and determination of n-alkylamines were investigated with anionic aldehydes to form water-soluble Schiff bases by using reversed-phase high-performance liquid chromatography (RP-HPLC). Two labeling reagents of salicylaldehyde-5-sulfonate (SAS) and 4-(4-sulfophenylazo)-1-hydroxy-2-naphthaldehyde (SPAHNA) were investigated. Sample solution containing the analytes and reagent solution were simultaneously injected and merged in the flow line, and water-soluble Schiff bases were formed in the reaction tube with its length of 5 m and at 70°C. The Schiff bases were resolved with water-methanol eluent on a reversed-phase column and photometrically detected. The entire analysis time including on-line derivatization, column separation and detection was accomplished within 25 min with SAS and 18 min with SPAHNA. The determination range for the n-alkylamines are 0∼50 μM with the limit of detections at 0.5∼1.0 μM for SAS and 0.08∼0.20 μM for SPAHNA.
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Yoichi TAKEDA, Koji ISHIDA2004 Volume 53 Issue 7 Pages 729-734
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThe thin-layer chromatographic behavior of all rare earths, except for promethium on carboxymethyl cellulose in aqueous sodium chloride solutions, has been surveyed as a function of the concentration of the salt to develop a new system for the separation of rare earths. It is reasonable to suppose that the competitive cation exchange between the solvent cations and the rare earths, the surface complexation of the rare earths with the carboxymethyl groups, and the salting-out effect of the solvent used, and moreover a change in the inner sphere coordination numbers across the rare earth series, play important roles in determining the Rf values of the metals in the present system. Yttrium, which generally belongs to heavier rare earths, has been separated from all of the rare earths, except for lanthanum, which provides Rf values similar to those of yttrium.
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Technical Paper
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Chihiro JIN, Kiyokazu FUKUDA, Haruhiko SATOH, Akira SAITOH2004 Volume 53 Issue 7 Pages 735-741
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThe clinical analysis of kidney or gallstones is important, not only to obtain qualitative data, but also to obtain the proportions of the main components such as calcium oxalate, calcium phosphate, cholesterol and Calcium bilirubinate. For the rapid analysis of stones, an auto-identification system for kidney and gallstones was developed using FT-IR and the Smart Tech technique, a modified reflection analysis method. The sample stone is rubbed on a metal plate and the plate set into the Smart Tech accessory. The metal sample plate is irradiated with IR light and the spectrum of the sample is obtained without making a KBr pellet. The Smart Tech accessory is an automated sample-measurement system, and up to six hundred samples can be sequentially analyzed by this system. In addition, a dedicated software to identify and quantify the measured samples was developed to simultaneously identify and quantitatively analyze the kidney or gallstones. This paper demonstrates a good correlation between the conventional KBr pellet method and this automated system.
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Note
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Hydrogen Hβ line as an internal standard in inductively coupled plasma optical emission spectrometryYûetsu DANZAKI, Kazuaki WAGATSUMA2004 Volume 53 Issue 7 Pages 743-748
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSAn internal standard element has generally been employed to obtain accurate analytical results in inductively coupled plasma-optical emission spectrometry (ICP-OES). This paper describes the possibility of hydrogen Hβ line (486.13 nm) being used as an internal standard line in ICP-OES. For this purpose, the relative intensities of a V II emission line were measured under various conditions when the Hβ line as well as the Y II 371.03-nm line were employed as the internal standard. The intensity variation of the V II line could be corrected more accurately by using the Hβ line rather than the Y II line. It should be noted that the intensity of the Hβ line is relatively weak and is easily affected by background emissions, which may lead to a large error in the estimation of the Hβ line intensity. Nevertheless, the Hβ line would be useful to correct for any variations of the sample amount introduced into ICP. The Hβ internal standard was applied to the determination of alloyed elements in Cu-In-Sn, Mo-Si-B, and Ge-Cr-Al-Ce-Sn.
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Hideaki MATSUE, Chushiro YONEZAWA2004 Volume 53 Issue 7 Pages 749-751
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSMulti-element determination in reference materials of soils (JSAC 0401, JSAC 0411) and sediments (NMIJ CRM 7302-a, NMIJ CRM 7303-a), which were prepared at the Japan Society for Analytical Chemistry and the National Institute of Advanced Industrial Science and Technology of the National Metrology Institute of Japan, respectively, has been carried out by neutron-induced prompt gamma-ray analysis (PGA) using standard addition and k0-standardization methods. Firstly, the absolute Ti concentrations in the samples were determined accurately by the standard addition method. Secondly, the relative multi-element concentrations were determined by the k0-standardization method. Finally, the absolute multi-element concentrations were obtained by normalizing the relative multi-element concentrations with the absolute Ti concentration in the samples. The 15 elements, such as H, B, Na, Si, S, Cl, K, Ca, Ti Cr, Mn, Fe, Cd, Sm and Gd were determined by k0-PGA. The analytical results of these reference materials agreed with the certified or reference values within about 10%.
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Hiroyuki IDA, Jun KAWAI2004 Volume 53 Issue 7 Pages 753-755
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSApplications of X-ray fluorescence spectrometry with a pyroelectric X-ray generator were studied. The X-ray generator with a pyroelectric crystal has unique features, such as small dimensions, low power, battery drive and a production of a periodically changing X-ray flux. Paint and leather samples were analyzed with this novel X-ray generator, and the performance of this device as an X-ray source for X-ray fluorescence spectrometry was investigated.
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Technical Letter
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Yûetsu DANZAKI, Kazuaki WAGATSUMA2004 Volume 53 Issue 7 Pages 757-761
Published: 2004
Released on J-STAGE: October 22, 2004
JOURNAL FREE ACCESSThis paper presents dissolution methods of several B-containing alloys to determine the amounts of B accurately by ICP-OES. It should be principally noted that boron is easily volatilized when the samples are dissolved in acid solutions, which may cause a serious error of the analytical result. Fe-B, Mn-Al-B, and Al-Pd-Mn-B alloy samples (30 mg) were dissolved in TEFE beakers by heating in 25 ml of an acid mixture : H3PO4 : HNO3 : HCl : H2O = 1 : 2 : 2 : 5. A Nd-Fe-B- Si alloy sample (100 mg) was dissolved in a TEFE beaker by heating in 30 ml of an acid mixture : H3PO4 : HNO3 : HCl : H2O = 1 : 2 : 2 : 5 and 4 ml of NaOH solution (8 mg/ml). The NaOH addition can prevent Si in the solution from precipitating because silicic acid can be dissolved in alkaline solutions. An Fe-Co-Nd-B alloy sample (30 mg) was dissolved in a TEFE beaker by heating in 30 ml of an acid mixture : HNO3 : guliceline : H2O = 15 : 0.3 : 14.7. A Nb-B alloy sample (100 mg) was dissolved in a polypropylene flask in 30 ml of HNO3 (1 + 1) and 2 ml of HF at room temperature. An Fe-Zr-Co-Ni-B sample (50 mg) was dissolved in a polypropylene flask in 35 ml of an acid mixture : HNO3 : HF : guliceline : H2O = 15 : 2 : 0.1 : 17.9 at room temperature. Ni-Al-Hf-B and Ni-Al-Ta-B alloy samples (40 mg) were dissolved in a TEFE beaker by heating in 35 ml of an acid mixture : HNO3 : HF : H2O = 15 : 2 : 18 and 5 ml of mannitol (1 w/v%).
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