Analytical Sciences
Online ISSN : 1348-2246
Print ISSN : 0910-6340
ISSN-L : 0910-6340
Volume 31 , Issue 9
Showing 1-14 articles out of 14 articles from the selected issue
Reviews
  • Kae SATO
    Type: Reviews
    2015 Volume 31 Issue 9 Pages 867-873
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    Microfluidic devices enable the miniaturization, integration, automation, and parallelization of chemical and biochemical processes. This new technology also provides opportunity for expansion in the field of cellular pathology. Fluorescence in situ hybridization (FISH) is a well-known gene-based method to image genetic abnormalities. Development of a FISH microfluidic platform has offered the possibility of automation with significant time and cost reductions, which overcomes many drawbacks of the current protocols. Microfluidic devices are also powerful tools for single-cell analysis. Capturing the circulating tumor cells (CTCs) from blood samples is one of the most promising approaches to enable the early diagnosis of cancer. The microfluidic devices are also useful to isolate rare CTCs at high efficiency and purity. In this review, I outline recent FISH and CTC analyses using microfluidic devices, and describe their applications for the cellular diagnosis of cancers.
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Original Papers
  • Yuko UENO, Kazuaki FURUKAWA, Andrew TIN, Hiroki HIBINO
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 875-879
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    We propose a molecular design for a biomolecular probe to realize an on-chip graphene oxide (GO) aptasensor with enhanced sensitivity. Here, GO works as an excellent acceptor for fluorescence resonance energy transfer. We inserted a rigid double-stranded DNA as a spacer between the GO surface and the aptamer sequence to extend the distance between a fluorescence dye and the GO surface during molecular recognition. We examined the dependence of the sensitivity on the length of the spacer quantitatively by using a 2×2 linear-array aptasensor. We used the modified aptamer with 10 and 30 base pair (bp) double-stranded DNA spacers. The signal with a 30bp-spacer was about twice as strong that with a 10bp-spacer as regards both thrombin and prostate specific antigen detections. The improvement in the sensitivity was supported by a model calculation that estimated the effect of spacer length on fluorescence recovery efficiency.
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  • Michiko AKIMARU, Kohei OKUBO, Yuki HIRUTA, Hideko KANAZAWA
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 881-886
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    We have developed a novel solid-phase extraction (SPE) system utilizing a temperature-responsive polymer hydrogel-modified stationary phase. Aminopropyl silica beads (average diameter, 40 – 64 μm) were coated with poly(N-isopropylacrylamide) (PNIPAAm)-based thermo-responsive hydrogels. Butyl methacrylate (BMA) and N,N-dimethylaminopropyl acrylamide (DMAPAAm) were used as the hydrophobic and cationic monomers, respectively, and copolymerized with NIPAAm. To evaluate the use of this SPE cartridge for the analysis of drugs and proteins in biological fluids, we studied the separation of phenytoin and theophylline from human serum albumin (HSA) as a model system. The retention of the analytes in an exclusively aqueous eluent could be modulated by changing the temperature and salt content. These results indicated that this temperature-responsive SPE system can be applied to the pretreatment of biological samples for the measurement of serum drug levels.
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  • Takayo MORIUCHI-KAWAKAMI, Minako OBITA, Toshiki TSUJINAKA, Yasuhiko SH ...
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 887-893
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    Nickel(II) complexes of [14]tetraazaannulene derivatives incorporating aromatic rings into their azaannulene framework were synthesized, and the anion-selectivity of the [14]tetraazaannulene nickel complexes 14 was evaluated by potentiometric measurements with solvent polymeric membrane electrodes. All of the [14]Tetraazaannulene nickel complexes, except 3, were found to exhibit high selectivity for the I ion over the SCN ion, although considerable interference of the ClO4 ion was observed in all 14 complexes. Concerning the anion-selectivities of 1 and 4, the incorporation of naphthalene rings into the azaannulene framework decreased not only the interference of the ClO4 ion but also the I ion-selectivity over the SCN ion. Comparison studies between the dibenzotetraaza[14]annulene nickel complexes 13 indicated that differences in the attached substituents of the [14]tetraazaannulene nickel complexes greatly influenced the ion-selectivity as ionophores. According to our computational results, the ionophoric properties of [14]tetraazaannulene nickel complexes 14 were influenced by their electrostatic properties rather than their topological properties.
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  • Tomoko FUKUUCHI, Noriko YAMAOKA, Kiyoko KANEKO
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 895-901
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    To evaluate cellular uptake and purine transport, we developed a high-performance liquid chromatography method for intra- and extracellular purine quantification. Our aim was to develop an effective method for simultaneously quantifying the substrate and metabolites with high sensitivity. C18 columns from different manufacturers were tested for simultaneous quantification of 22 different purine bases, nucleosides, and nucleotides. We used a YMC-Triart C18 column. The analysis conditions, including extraction solutions for the cells and cell culture medium, were optimized to achieve good quantification. Linearity, accuracy, determination limits, and recovery were assessed and showed good performance. The developed HPLC method was successfully applied to the qualitative analysis of 22 different intra- and extracellular purines, demonstrating that it is useful for studying the overall pattern of purine metabolism. This method could also be useful for evaluating metabolic dynamics of purines under a variety of stimulatory conditions of culture cells.
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  • Liangmian CHEN, Akira KOTANI, Hideki HAKAMATA, Risa TSUTSUMI, Yuzuru H ...
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 903-909
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    We have proposed an assessment methods to estimate the measurement relative standard deviation (RSD) of chromatographic peaks in quantitative HPLC for herbal medicines by the methodology of ISO 11843 Part 7 (ISO 11843-7:2012), which provides detection limits stochastically. In quantitative HPLC with UV detection (HPLC-UV) of Scutellaria Radix for the determination of baicalin, the measurement RSD of baicalin by ISO 11843-7:2012 stochastically was within a 95% confidence interval of the statistically obtained RSD by repetitive measurements (n = 6). Thus, our findings show that it is applicable for estimating of the repeatability of HPLC-UV for determining baicalin without repeated measurements. In addition, the allowable limit of the “System repeatability” in “Liquid Chromatography” regulated in a pharmacopoeia can be obtained by the present assessment method. Moreover, the present assessment method was also successfully applied to estimate the measurement RSDs of quantitative three-channel liquid chromatography with electrochemical detection (LC-3ECD) of Chrysanthemi Flos for determining caffeoylquinic acids and flavonoids. By the present repeatability assessment method, reliable measurement RSD was obtained stochastically, and the experimental time was remarkably reduced.
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  • Mika TADA, Yoshimi NIWANO, Masahiro KOHNO
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 911-916
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    Nitroxide radical formations of deferoxamine mesylate (DFX) that is used clinically to treat iron-overload patients was examined by a tyrosine-tyrosinase reaction system as models of the H-atom transfer or proton-coupled electron transfer. When DFX was exposed to the tyrosine-tyrosinase reaction, nine-line ESR spectrum (g = 2.0063, hfcc; aN = 0.78 mT, aH(2) = 0.63 mT) was detected, indicating that the oxidation of DFX leads to a nitroxide radical. The signal intensity of the DFX radical increased dependently on the concentrations of tyrosine and tyrosinase. The amounts of DMPO-OH spin adducts via the tyrosine-tyrosinase reaction declined with DFX. Furthermore, mass spectra of an extra removed from the tyrosine-tyrosinase reaction mixture showed that the enzyme reactions might not be degradations of DFX. Therefore, there might be two types of DFX reaction passways, which could be through an internal electron transfer from tyrosine and hydrogen absorptions by ·OH directly.
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  • Maria ATANASSOVA, Vanya KURTEVA, Isabelle BILLARD
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 917-922
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    Two Eu(III) complexes were synthesized using 4-acylpyrazolone ligands: 3-methyl-4-(4-methylbenzoyl)-1-phenyl-pyrazol-5-one (HPMMBP) and 3-methyl-1-phenyl-4-(4-phenylbenzoyl)-pyrazol-5-one (HPPMBP). The composition of the obtained solid complexes was determined as Eu(PMMBP)3·C2H5OH and Eu(PPMBP)3·3H2O based on elemental analysis and was further studied by IR, NMR and TG-TSC data. The lanthanoid complexation in solid state and in solution during liquid-liquid extraction (molecular diluent and ionic liquid) is discussed.
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  • Etsuko NAKAMURA, Yuki HIRUTA, Takafumi WATANABE, Naoko IWASAWA, Daniel ...
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 923-928
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    The properties of a fluorous solvent extraction system for trivalent lanthanide metal ions are reported. A fluorinated extractant, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluoro-1-(2-thienyl)-1,3-nonanedione, and HFE-7200 (C4F9OC2H5) as the extraction solvent were chosen. With this fluorous extractant/solvent combination, higher extraction ratios and separation factors compared to a conventional organic solvent system (thenoyltrifluoroacetone in CHCl3) were achieved for 5 heavy lanthanide ions (Lu, Yb, Tm, Er and Ho). On the other hand, light lanthanide ions (Nd, Pr, Ce and La) are hardly extracted, therefore enabling the mutual separation of light lanthanides from middle or heavy lanthanide ions.
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  • Yuko NISHIMOTO, Hiroki EGUCHI, Eita SHIMODA, Toshiyuki SUZUKI
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 929-934
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    The gelation of aqueous methylcellulose (MC) solutions containing polyethylene glycol (PEG) was studied by the combination of differential scanning calorimetry (DSC) and Raman spectrometry. The gelation of MC hydrogels containing PEG occurred in two-steps. First, the gel network was formed by the hydrophobic interaction between MC and PEG at 310 – 313 K, and then, the gel network was formed between MC chains at 323 K. On the other hand, in the MC hydrogels containing PEG and NaCl, sodium ion assumed to be enclosed by PEG, forming a helix with the hydrophobic groups outward. The sodium ion in the gel was expected to be surrounded by the ether oxygen of PEG as crown ether.
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  • Kiyoko KANEKO, Shin-ichiro NISHII, Yoko IZUMI, Makoto YASUDA, Tomoyo Y ...
    Type: Original Papers
    2015 Volume 31 Issue 9 Pages 935-942
    Published: September 10, 2015
    Released: September 10, 2015
    JOURNALS FREE ACCESS
    In this study, we performed proteomic analysis following sequential protein extraction on calcium oxalate monohydrate (COM) and calcium oxalate dihydrate (COD) urinary stones to determine the specific matrix proteins according to the crystal components of the stones. After X-ray and IR analysis of 13 urinary stones, matrix proteins were sequentially extracted with KCl, formic acid, guanidine-HCl, and EDTA, before SDS-electrophoresis followed by liquid chromatography–mass spectrometry/mass spectrometry (LC-MS/MS). The electrophoretic patterns of the extracted proteins differed from that of COM and COD stones. LC-MS/MS identified 65 proteins, of which many were cellular plasma proteins, and were frequently detected regardless of the crystal components. However, 6 proteins (protein Z, protein S, prothrombin, osteopontin, fatty acid binding protein 5, and ubiquitin) were detected in the final EDTA fractions of COM stones. These proteins are involved in the coagulation process or osteometabolism, and thus the roles they play are of particular interest.
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